Single-functional and mixtures of multi-functional oligomeric performance additive compositions and their uses

ABSTRACT

The present invention comprises novel single-functional and mixtures of multi-functional oligomeric performance additive compounds having one or more components of Structure A R1 ? ? ##STR1## (The definitions of R, Z1, Z2, Z3, A1, A2, A3 and y are given in the Summary Section), their uses and polymeric compounds and compositions containing them which have enhanced oxidative stabilities, enhanced ultraviolet (UV) and light stabilites and/or enhanced flame retardance. An example is the bis sulfonic acid bispotassium salt reaction product from an oligomeric caprolactone diol (TONE® 260), 2-sulfobenzoic acid anhydride and potassium carbonate, and use of this product, at levels up to about 3.0%, in a general purpose bisphenol A polycarbonate resin, to enhance the fire resistance or flame retardance of the polycarbonate resin.

CROSS REFERENCE TO RELATED APPLICATION

This is a division of co-pending U.S. patent application Ser. No.137,989, filed Dec. 24, 1987, now U.S. Pat. No. 5,013,777 issued May 7,1991.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel single-functional and mixtures ofmulti-functional oligomeric performance additive compounds, their usesand polymeric compounds and compositions containing them which haveenhanced oxidative stabilities, enhanced ultraviolet (UV) and lightstabilities ad/or enhanced flame retardance properties.

As a result of research relating to the above-identified oligomericperformance additive compounds, the inventors have discovered thatcertain sulfobenzoic acids, esters and their salts have a previouslyundiscovered use as flame retardant additives to oligomers and polymers,and particularly as additives to aromatic polycarbonates.

2. Definitions

To aid in understanding the present invention, the following definitionsof terms used in the description and/or claims are set forth:

"Single-Functional Oligomeric Performance Additive"--An oligomericcompound or composition having a single (one) type of performanceadditive function (e.g., UV stabilizer, light stabilizer, flameretardant or antioxidant stabilizer).

"Multi-functional Oligomeric Performance Additive"--An oligomericcompound or composition having more than one type of performanceadditive function.

"Non-fugitive"--An additive is non-fugitive if it does not leach out ofa thermoplastic polymeric resin to which it is added, either duringprocessing or during the end use of the thermoplastic resin to which theadditive has been added.

"Oligomer"--A compound or composition having two or more repeat units inits chemical structure, but usually does not include high polymershaving molecular weights above about 10,000.

3. Description of the Prior Art

Although thermoplastics (hereinafter generally referred to as"plastics") have many desirable properties and, consequently, a myriadof uses, they also suffer from deficiencies that can limit or evenprevent their use in certain applications. Some of the more commondeficiencies of plastics are that, 1) most can burn, 2) they are subjectto oxidative degradation during processing and end use, and, 3) they aresubject to degradation by light, and particularly by ultraviolet (UV)light. Therefore, in order to overcome these deficiencies, a widevariety of fire retardants, antioxidants and UV and light stabilizeradditives have been developed. In order to be successful, an additivemust be compatible with the plastic, i.e., it must not significantlyadversely affect physical properties that are important to the end user,and it must be non-fugitive. An important consideration is that approvalby the U.S. Food and Drug Administration of a plastic composition usedin food and related applications is easier to obtain when it contains anon-fugitive additive.

One general approach to compatible, non-fugitive additives is tocopolymerize them with the monomer(s) that constitute the plastic. Thiscan be accomplished in several ways. For example, a vinyl group can beattached to the performance additive, which in principle, can then becopolymerized with other vinyl monomers to form a copolymer with pendantperformance additives covalently attached. Alternately, performanceadditives possessing suitable functional groups, such as hydroxy, aminoor carboxy groups, can take part in condensation polymerizations to formpolymers, such as polyesters, polyamides, and polyurethanes, withattached performance additive groups.

One type of fire retardant additive for plastics is the halogenatedaromatic class of fire retardants. Thus, an example of acopolymerization of a fire retardant with a vinyl group attached is thecopolymerization of bromostyrene with a vinyl monomer, such as styrene.An example of condensation polymerization of a fire retardant with asuitable monomer is the copolymerization of tetrabromobisphenol A andbisphenol A with phosgene in the presence of base to form aco-polycarbonate.

One type of antioxidant additive is the hindered phenol class ofantioxidants. Vinyl ester derivatives of3-(3,5-di-t-butyl-4-hydroxypehnyl) propionic acid (HBPA) have beencopolymerized to form polyolefins with antioxidant bound to the polymer.Examples of this approach are disclosed in U.S. Pat. Nos. 3,708,520 and3,957,920. Diester derivatives of HBPA have also been used incondensation polymerizations to form polyesters with the additiveattached. Examples here are in U.S. Pat. Nos. 3,943,106; 3,951,915 and4,094,857.

There are many types of UV stabilizers for plastics, examples beingo-hydroxybenzophenones, cyanocinnamates, hindered amine lightstabilizers (HALS), 2-hydroxyphenylbenzotriazoles, dialkylbenzylidenemalonates, and oxanilides. Vinyl ester derivatives of2,4-dihydroxybenzophenones (DHBP) have been both homopolymerized andcopolymerized. This work is described in U.S. Pat. Nos. 3,313,866;3,365,421; 3,391,110; and 4,304,895. In addition, suitably substitutedDHBP derivatives such as 2-hydroxy-4-(2-hydroxyethoxy) benzophenone,have been used in condensation polymerizations as described in U.S. Pat.Nos. 4,418,000 and 4,264,680.

In the case of the cyanocinnamate class of stabilizers, various vinylester derivatives of 2-cyano-3,3-diphenyl-2-propenoic acid have beencopolymerized with different vinyl monomers as described in U.S. Pat.Nos. 4,276,136; 4,207,253 and 4,202,834. vinyl monomers of HALS are alsoknown and have been copolymerized with a variety of monomers. Examplescan be found in U.S. Pat. Nos. 4,175,970; 4,210,612 and 4,294,949. thereare also examples of HALS compounds used in condensation polymerizationsas disclosed in Canadian Patent 1,016,295. In these examples, a HALS isattached to an ethylene oxide oligomer, which in turn is copolymerizedwith diethylene glycol terephthalate to form a polyethyleneterephthalate polyester with a HALS group incorporated into it.

Although the above approaches do incorporate a non-fugitive additiveinto a plastic, there are still some drawbacks. For instance, additiveswith a vinyl or other suitable functional group may not be readilyavailable, the reactive additive may not copolymerize easily with thedesired monomers, or the resultant copolymer may be deficient in otherphysical properties (such as impact strength) that are important to theend user.

Instead of the foregoing approaches for incorporating non-fugitiveadditives in plastics, in accordance with the inventive concept of thepresent invention, a performance additive is attached onto an oligomerhaving a molecular weight of less than about 10,000, typically, lessthan about 5,000, and then the oligomer-additive adduct is blended withthe desired polymer. By judicious choice of oligomers, the compatibilityof the oligomer-additive adduct with a polymer can be assured, and withrelatively high molecular weight of the adduct, its non-fugitive naturein a polymer blend is also assured.

In order to use this approach, suitable reactive functional groups atone end, at both ends and/or on branch points along the oligomer arerequired. Thus, mono-, di- or polyadducts can be prepared and blendedwith the chosen polymer. Examples of suitable functional groups on anoligomer are groups such as acid halide, amino, anhydride, carboxy,chloroformate, epoxy, hydroxy, and isocyanate.

These same types of functional groups may also be present on theadditive. Thus, chemical attachment of the additive onto the oligomer isassured by incorporating functional groups onto the additive that areknown in the art to react with those on the oligomer. One example is anadditive with acid halide (chloride for instance) groups being reactedwith an oligomer possessing hydroxy groups to form an oligomer-additiveadduct held together by the resultant ester linkages.

Polymers including fire retardant functional groups are known in theprior art. One particular type has aromatic sulfonic acid salts as theretardant functional group. These are effective fire retardants foraromatic polycarbonates (PC's). Examples of polymeric salts arepolysulfonated salts of polysulfone and polysulfone copolymers which aredescribed in U.S. Pat. Nos. 4,033,930; 4,092,294 and 3,948,851. In U.S.Pat. No. 3,978,024, sulfonated salts or aromatic polycarbonates aredisclosed, while in U.S. Pat. No. 4,032,506 polysodiumpoly(2,6-di-methyl-phenylene oxide) polysulfonate is mentioned.Sulfonated salts of polymers with aralkenylidene moieties are disclosedin U.S. Pat. Nos. 3,940,366 and 3,933,734. In U.S. Pat. No. 3,951,910,sulfonic acid salts of a variety of polymers are described. The aboveexamples all share the common thread of a polymer being sulfonated witha suitable sulfonating agent such as sulfur trioxide or fuming sulfuricacid. However, there are only a few examples of a sulfonic acid saltbeing incorporated into a polymer using other types of reagents.

The prior art does not disclose the use of 2-sulfobenzoic acidcompounds, such as 2-sulfobenzoic acid cyclic anhydride and relatedcompounds of the present invention as reagents for polymers or oligomerscontaining mono-, di-, and polyhydroxy functional groups. When thisadditive and a hydroxy or amino oligomer are allowed to react in thepresence of base, the resulting compounds are polymers or oligomerswhich have one or more arylsulfonic acid salt groups attached to them.Such compounds are fire retardant additives according to the presentinvention useful for aromatic polycarbonates (PC's).

Thus, in the case of sulfonic acid salt fire retardants, it is believedthat the closest prior art to the present invention is disclosed in U.S.Pat. Nos. 3,933,734 and 4,285,855 where propane sulfone is used as anendcapping agent for polymers. The products are polymers endcapped withalkylsulfonic acid groups. These are fire retardant additives foraromatic (PC's).

In the case of UV stabilizers, the closest prior art to the presentinvention is believed to be disclosed is U.S. Pat. Nos. 4,260,719 and4,247,474 where cyanocinnamate types of UV stabilizer,1-cyano-3,3-diphenyl-2-propenoyl chloride and2-(chlorocarbonyloxy)ethyl-2-cyano-3,3-diphenylacrylate are used toendcap polycarbonate.

In the case of antioxidants, the closest prior art to the presentinvention is believed to be disclosed in U.S. Pat. Nos. 3,944,594 and4,032,562, and Canadian Patent 995686 where polyethylene oxide esters ofHBPA are disclosed as antioxidants for plastics. In U.S. Pat. No.3,819,573 HBPA was attached to aliphatic polyesters or polyamides byheating either it or its methyl or ethyl ester derivatives in thepresence of suitable monomers or oligomers, such as caprolactone andcaprolactam and oligomers therefrom.

The prior art does not disclose the endcapping of aliphatic polyester,polycarbonate, polyamide, polyurethane and polyurea oligomers. Inaddition, polyether-polythioether co-oligomers, amino terminatedplyethers and hydroxy- or amino-terminated silicones or siliconecopolymers have not been disclosed, nor have been disclosed hydroxyterminated polyethylene oligomers, amino- or hydroxy-terminatedpolybutadiene oligomers, amino- or hydroxy-terminatedpolybutadiene-acrylonitrile oligomers, or styrene-allyl alcoholco-oligomers. In this invention, the above oligomers can be endcappedwith suitable fire retardants, antioxidants, light and/or UVstabilizers, and the resultant oligomer-additive adduct can be blendedinto a compatible polymer so as to improve the fire retardance and/oroxidative stability and/or light and/or UV stability of the polymer.

SUMMARY OF THE INVENTION

The present invention comprises in one aspect novel single-functionaland mixtures of multi-functional oligomeric performance additivecompounds having one or more components of Structure A: ##STR2## where

y=0 to 75,

Z1, Z2 ad Z3 are the same or different with the proviso that at leastone of Z1, Z2 and Z3 is selected from the group consisting of at leastone of performance additive functional group I, II, III and IV, wherein

performance additive functional group I is an antioxidant monoradicalhaving a structure selected from the group consisting of structure (1),(2) and (3): ##STR3## where

X is selected from the group consisting of NH and O,

R1 and R2 are the same or different and each is an alkyl radical of 1 to13 carbons, preferably a t-alkyl radical of 4 to 8 carbons or at-aralkyl radical of 9 to 13 carbons,

R11 is selected from the group consisting of nothing and an alkylenediradical of 1 to 6 carbons, preferably 1 to 3 carbons, Z is 0 or 1; and##STR4## where R3 is selected from the group consisting of an alkylradical of 1 to 18 carbons, an aryl radical of 6 to 12 carbons and anaralkyl radical of 7 to 11 carbons; and ##STR5## where

R3 and R3' are the same or different, and

R3' is selected from the group consisting of an alkyl radical of 1 to 18carbons, an aryl radical of 6 to 12 carbons and an aralkyl radical of 7to 11 carbons;

performance additive functional group (II) is a UV stabilizingmonoradical having a structure selected from the group consisting ofstructure (1), (2), (3) and (4): ##STR6## where

X1 is selected from the group consisting of nothing and O, and

R_(b) is selected from the group consisting of hydrogen and asubstituent selected from the group consisting of a lower alkyl radical,a lower alkoxy radical, a cyano radical, chloro, bromo and nitro;##STR7## where

R_(b) ' is selected from the group consisting of hydrogen and asubstituent selected from the group consisting of a lower alkyl radical,a t-octyl radical, an α-cumyl radical, a lower alkoxy radical, a cyanoradical, chloro, bromo and nitro;

performance additive functional group (III) is a light stabilizingmonoradical having a structure: ##STR8## where

X and X2 are the same or different and each is selected from the groupconsisting of HN and O, and

R4 is selected from the group consisting of H, a lower alkyl radical, anacyl of 2 to 18 carbons, an aroyl radical of 7 to 15 carbons, analkoxycarbonyl radical of 2 to 19 carbons, and an aryloxy-carbonylradical of 7 to 15 carbons; and

performance additive functional group (IV) is a flame retardantmonoradical having a structure selected from the group consisting ofstructure (1), (2), (3), (4), (5) and (6): ##STR9## where

Q is selected from the group consisting of H, Cl and Br and

M is selected from the group consisting of H, an alkali metal and analkaline earth metal; ##STR10## where

R5 is an alkyl radical of 1 to 12 carbons,

Q' is selected from the group consisting of Cl and Br, and

t is 0 to 15; ##STR11## where R22 is selected from a group consisting ofan alkylene diradical of 1 to 4 carbons, a 1,3-phenylene diradical and a1,4-phenylene diradical; ##STR12## where t1 is 1 to 5; and ##STR13##

Any other of Z1, Z2 and Z3 not selected from the group consisting ofperformance additive functional groups I, II, III and IV is selectedfrom the group consisting of hydroxy amino, at least one substitutedradical and an unsubstituted radical, where the radical is selected fromthe group consisting of an alkoxy radical of 1 to 12 carbons, analkylamino radical of 1 to 12 carbons, an acyloxy radical of 1 to 12carbons, an acylamino radical of 1 to 12 carbons, an alkenoyloxy radicalof 3 to 12 carbons, an alkenoylamino radical of 3 to 12 carbons, anaroyloxy radical of 7 to 15 carbons, an aroylamino radical of 7 to 15carbons, a phthalimido radical, an alkoxycarbonyloxy radical of 2 to 13carbons, an alkoxycarbonylamino radical of 2 to 13 carbons, analkenyloxycarbonyloxy radical of 3 to 12 carbons, analkenyloxycarbonylamino radical of 3 to 12 carbons, anaryloxycarbonyloxy radical of 7 to b 15 carbons, an aryloxycarbonylaminoradical of 7 to 15 carbons, an alkylaminocarbonyloxy radical of 2 to 13carbons, an arylaminocarbonyloxy radical of 7 to 15 carbons, anaralkylaminocarbonyloxy radical of 7 to 16 carbons, an alkylsulfonyloxyradical of 1 to 8 carbons, an alkylsulfonylamino radical of 1 to 8carbons, an arylsulfonyloxy radical of 6 to 11 carbons, anarylsulfonylamino radical of 6 to 11 carbons, a perfluoroacyloxy radicalof 2 to 14 carbons, and a perfluoroacylamino radical of 2 to 14 carbons;where the substituents thereof are selected from the group consisting ofCl, Br, an acetyl radical, an alkyl radical of 1 to 6 carbons, analkenyl radical of 2 to 6 carbons, an aryl radical of 6 to 10 carbons,an alkoxy radical of 1 to 6 carbons, an aryloxy radical of 6 to 10carbons, an alkoxycarbonyl radical of 2 to 13 carbons, ahydroxyalkoxycarbonyl radical of 3 to 13 carbons, achlorohydroxyalkoxycarbonyl radical of 4 to 13 carbons, and anepoxyalkoxycarbonyl radical of 4 to 13 carbons;

A1, A2 and A3 are nothing, the same or different, with the proviso thatwhen A3 is nothing, only one of A1 and A2 can be nothing, and

when y=0,

A2 is nothing, and

A1 is selected from the group consisting of diradicals (1), (2), (3),(4) and (5): ##STR14## where

R33 is selected from the group consisting of an alkylene diradical of b2 to 8 carbons and an alkylene diradical of 2 to 8 carbons containing atleast one atom selected from the group consisting of O, S and N atoms inthe alkylene chain,

(Z1) and (Z2) show the relationship of the --A1-- diradical to Z1-- andZ2--, respectively, and

the sum of k and m is 3 to 50; ##STR15## where

(Z1) and (Z2) show the relationship of the --A1-- diradical to Z1 andZ2, respectively, and

n1 is 5 to 20; ##STR16## where

R6 is selected from the group consisting of H and a methyl radical,

(Z1) and (Z2) show the relationship of the --A1-- diradical to Z1 andZ2, respectively,

n2 is 2 to 15 and

n3 is 0 to 3; ##STR17## where

R4' is selected from the group consisting of H and a lower alkylradical,

(Z1) and (Z2) show the relationship of the --A1-- diradical to Z1 andZ2, respectively, and

n4 is 2 to 70; and

(5) an aligomeric diradical selected from the group consisting of anoligomeric polybutadiene diradical, an oligomeric aliphatic polyesterdiradical an oligomeric polycaprolactone diradical, an oligomericaromatic polyester diradical, an oligomeric aliphatic polycarbonatediradical, an oligomeric aliphatic polyamide diradical, an oligomericaliphatic polyurethane diradical, an oligomeric aliphatic polyureadiradical, an oligomeric bisphenol A polycarbonate diradical, anoligomeric tetrabromobisphenol A polycarbonate diradical and anoligomeric bisphenol A-tetrabromobisphenol A co-polycarbonate diradical;and

when y is 1,

the triradical ##STR18## has a structure: ##STR19## where

(Z1), (Z2) and (Z3) show the relationship of the triradical to Z1, Z2,and Z3, respectively,

R7 is selected from the group consisting of H and an alkyl radical of 1to 6 carbons,

R44 is selected from the group consisting of nothing and an alkylenediradical of 1 to 6 carbons, and

the sum of k1, m1 and p1 is 2 to 20;

when y is 2 is 75,

A1 has a structure: ##STR20## where

R8 is selected from the group consisting of a phenyl radical and anacetoxy radical, and

s1 is 4 to 25; and

when y is 2 to 75,

A2 and A3 are nothing, and

triradical R has a structure: ##STR21## where p R9 is selected from thegroup consisting of nothing and a methylene diradical, (Z3) shows therelationship between the triradical R group and Z3;

the compound of Structure A being preparable from a compound ofStructure B: ##STR22## where

T is selected from the group consisting of H and a halocarbonyl radical;

where the compound of Structure B is reacted with a performance additivecompound possessing at least one co-reactive group selected from thegroup consisting of a hydroxy radical, an amino radical, an epoxideradical, a carboxylic acid cyclic anhydride radical, a sulfocarboxyliccyclic acid anhydride radical, a haloformate radical and an isocyanateradical.

Another aspect of the present invention relates to novel processes forenhancing the flame retardance, UV stability, light stability and/oroxidative stability of engineering thermoplastic polymeric resins, suchas aromatic polycarbonates (PC's); PC's blended with styrene maleicanhydride (SMA) copolymers; PC's blended with acrylonitrile butadienestyrene (ABS) copolymers; polyethylene terephthalate (PET); polybutyleneterephthalate (PBT); polyphenylene oxide and its blends with polystyrene(PS) and high impact polystyrene (HIPS); styrene maleic anhydride (SMA)copolymers; acrylonitrile butadiene styrene (ABS) copolymers;polyethylene terephthalate (PET) blended with polybutylene terephthalate(PBT); nylons; polysulfones; etc.; by mixing about 0.05% to 10% byweight based on the weight of the engineering thermoplastic resin, ofthe novel single-functional and mixtures of multi-functional oligomericperformance additive compounds having one or more components ofStructure A, at about 100° C. to 550° C., preferably about 150° C. toabout 400° C., until intimately mixed.

Still another aspect of the present invention relates to novelcompositions having enhanced flame retardance, UV stability, lightstability and/or oxidative stability comprising about 0.05% to about 10%by weight, based on the weight of the engineering thermoplasticpolymeric resin, of the novel single-functional and mixtures ofmulti-functional oligomeric performance additive compositions having oneor more components of Structure A and about 90% to about 99.95% of atleast one engineering thermoplastic polymeric resin, such as thoseresins and resin blends set forth above with respect to the process forenhancing the indicated performance properties. The performanceadditives become non-fugitive components of the engineeringthermoplastic polymeric resin compositions.

Yet another aspect of the present invention relates to a process ofproducing a flame retardant aromatic polycarbonate resin compositioncomprising blending with the polycarbonate resin composition a compoundhaving a Structure C: ##STR23## where

R10 is selected from the group consisting of:

an unsubstituted alkyl radical of 1 to 30 carbons, a substituted alkylradical of 1 to 30 carbons, an unsubstituted aryl radical of 6 to 12carbons, a substituted aryl radical of 6 to 12 carbons, an unsubstitutedaralkyl radical of 7 to 16 carbons, a substituted aralkyl radical of 7to 16 carbons, an unsubstituted biphenyl radical of 12 to 20 carbons anda substituted biphenyl radical of 12 to 20 carbons, where thesubstituents are selected from the group consisting of fluorine,chlorine and bromine, where the maximum number of substituents perradical does not exceed 12; and

a UV stabilizing monoradical having a structure selected from the groupconsisting of structure (1), (2), (3) and (4): ##STR24## where

R3 is selected from the group consisting of an alkyl radical of 1 to 18carbons, an aryl radical of 6 to 12 carbons and an aralkyl radical of 7to 11 carbons;

R11 is an alkylene diradical of 1 to 6 carbons;

z is 0 or 1;

X is selected from the group consisting of NH and O, and

R_(b) is selected from the group consisting of hydrogen and asubstituent selected from the group consisting of a lower alkyl radical,a lower alkloxy radical, a cyano radical, chloro, bromo and nitro; and##STR25## where

R_(b), is selected from the group consisting of hydrogen and asubstituent selected from the group consisting of a lower alkyl radical,a t-octyl radical an α-cumyl radical, a lower alkoxy radical, a cyanoradical, chloro, bromo and nitro;

the compound of Structure C being present in an amount effective toprovide flame retardance to the polycarbonate resin composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preparation of NovelSingle-Functional and Mixtures of Multi-Functional OligomericPerformance Additive Compounds

The novel single-functional and mixtures of multi-functional oligomericperformance additive compounds of Structure A of this invention can beprepared by either reacting the performance additive functional groups,namely antioxidants (AO's), UV stabilizers, light stabilizers and/orflame retardants, possessing reactive acid halide, acid anhydride orhaloformate groups, with oligomeric mono- or poly-hydroxy or aminocompounds, or by reacting the performance additive functional groupspossessing hydroxy or amino groups with co-reactive mono- orpoly-haloformates (typically chloroformates) or mono- and poly-carbamoylhalides (typically carbamoyl chlorides) of oligomeric mono- orpoly-hydroxy and amino compounds, usually in the presence of basiccompounds.

In general, the basic compounds are inorganic bases, such as sodiumhydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate,potassium carbonate, sodium hydrogen carbonate and potassium hydrogencarbonate, and organic amines, such as pyridine, N,N-dimethylaniline,triethylamine, tributylamine and A1,4-diazabicyclo(2.2.2) octane.

AO's possessing acid halide or chloroformate reactive groups include,for example,

3,4-di-t-butyl-4-hydroxybenzoyl chloride,

3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl chloride,

3,5-di-t-butyl-4-hydroxybenzoyl bromide,

methylmercaptopropionyl chloride,

n-hexylmercaptopropionyl chloride,

n-dodecylmercaptopropionyl chloride,

n-octadecylmercaptopropionyl chloride,

n-hexylmercaptoacetyl chloride,

1,5-dichlorocarbonyl-3-thiapentane (i.e., the diacid dichloride ofmercaptodipropionic acid),

diethyl chlorophosphite,

2-(3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy)ethyl chloroformate,

2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)propyl chloroformateand

2-(3,5-di-t-butyl-4-hydroxybenzoyloxy)propyl chloroformate.

In general, these reactive AO's may be prepared by reacting thecorresponding antioxidant acid with an acid halogenating agent such asthionyl chloride, thionyl bromide, phosphorous trichloride, phosphorouspentachloride, phosgene (in the presence of N,N-dimethylformamide) andbenzotrichloride. Alternately, the reactive AO's may be prepared byreacting the corresponding antioxidant alcohol (e.g., 2-(3-(b3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy)ethanol) with phosgene,followed by isolation of the antioxidant acid halide or chloroformatefrom the reaction mixture.

The AO's with acid halide or chloroformate groups are co-reactive witholigomeric ono- and poly-hydroxy and amino compounds. The hydroxy groupon the phenyl ring of reactive hindered phenol AO's is relativelynon-reactive with acid halide or chloroformate groups.

AO's possessing hydroxy groups which are reactive with oligomers havingco-reactive chlorocarbonyl groups, e.g., mono- or polychloroformates ormono- and poly-carbamoyl chlorides of oligomeric mono- or poly-hydroxyand amino compounds, include, for example,2-(3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy)ethanol and2-(3,4-di-t-butyl-4-hydroxybenzoyloxy)propanol.

UV stabilizers possessing acid halide or chloroformate reactive groupsinclude, for example,

2-(4-benzoyl-3-hydroxyphenoxy)acetyl chloride,

2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate,

2-(4-benzoyl-3-hydroxyphenoxy)propyl chloroformate,

2-cyano-3,3-diphenyl-2-propenoyl chloride,

2-(2-cyano-3,3-diphenyl-2-propenoyloxy)ethyl chloroformate,

2-(2-hydroxy-4-(2-chlorocarbonylmethoxy)phenyl)-2H-benzotriazole,

2-(2-hydroxy-4-(2-chlorocarbonyloxyethoxy) phenyl)-2H-benzotriazole and

dimethyl or diethyl 3- or 4-chlorocarbonyloxyethoxybenzylidenemalonates.

UV stabilizers possessing hydroxy groups which are reactive witholigomers having co-reactive chlorocarbonyl groups, e.g., mono- orpoly-chloroformates, or mono- and poly-carbamoyl chlorides of oligomericmono- or poly-hydroxy ad amino compounds,, include, for example,

2-(4-benzoyl-3-hydroxyphenoxy)ethanol,

2-(4-benzoyl-3-hydroxy-phenoxy)propanol,

2-(2-cyano-3,3-diphenyl-2-propenoyloxy)ethanol,

2-(2-hydroxy-4-(2-hydroxyethoxy)phenyl)-2H-benzotriazole and dimethyl ordiethyl 3- or 4-(2-hydroxyethoxy) benzylidene malonates.

Light stabilizers possessing acid halide or chloroformate reactivegroups include, for example,4-chlorocarbonyloxy-2,2,6,6-tetramethylpiperdine hydrochloride and4-chlorocarbonyloxy-1,2,2,6,6-pentamethylpiperdine hydrochloride.

Light stabilizers possessing groups which are reactive with oligomershaving co-reactive chlorocarbonyl groups, e.g., mono- orpolychloroformates or mono- and poly-carbamoyl chlorides of oligomericmono- or poly-hydroxy and amino compounds, include, for example,4-amino-2,2,6,6-tetramethylpiperdine,4-amino-1,2,2,6,6-pentamethylpiperidine and1,2,2,6,6-pentamethyl-4-piperidiol.

Reactive fire retardant intermediates possessing acid anhydride, acidhalide or chloroformate reactive groups include, for example,

3,4,5,6-tetrachlorophthalic anhydride,

3,4,5,6-tetrabromophthalic anhydride,

2-sulfobenzoic acid anyhydride,

3,4,5,6-tetrabromo-2-sulfobenzoic acid anhydride,

3,4,5,6-tetrabromo-2-(ethoxy-carbonyl)benzoyl chloride,

3,4,5,6-tetrabromo-2-(3,6,9,12,15,18,21-heptaoxadocosoxycarbonyl)benzoyl chloride,

N-(chlorocarbonylmethyl)-3,4,5,6-tetrabromophthalimide,

4-bromophenyl choroformate,

2,4,6-tribromophenyl chloroformate and di(isopropylphenyl)chlorophosphate.

In general, cyclic carboxylic anhydrides, such as3,4,5,6-tetrachlorophthalic anhydride and 3,4,5,6-tetrabromophthalicanhydride, react with hydroxy compounds to form 2-carboxybenzoates (acidphthalates) which are usually unstable thermally. At elevatedtemperatures they decompose to produce the starting reactants, i.e., thealcohol and the cyclic carboxylic anhydride. In order to prevent thisfrom happening, the 2-carboxybenzoate is further esterified withalcohols or with epoxides to form the corresponding alkyl alkyl'phthalates or alkyl 2-hydroxyalkyl' phthalates. Epoxides useful in thisrespect include, for example, ethylene oxide, propylene oxide,1,2-butylene oxide, styrene oxide, cyclohexene oxide andepichlorohydrin.

Fire retardants possessing hydroxy groups which are reactive witholigomers having co-reactive chlorocarbonyl groups, e.g., mono- orpoly-chloroformates or mono- and poly-carbamoyl chlorides of oligomericmono- or poly-hydroxy and amino compounds, include, for example,4-bromophenol, 2,4,6-tribromophenol, the mono-potassium salt of2-sulfo-1,4-dihydroxybenzene,N-(2-hydroxyethyl)-3,4,5,6-tetra-bromophthalimide andethyl-2-hydroxypropyl-3,4,5,6-tetrabromophthalate.

When reacting the performance additive functional groups (AO's, UVstabilizers, light stabilizers and/or flame retardants) having acidchloride, acid anhydride and/or chloroformate groups with oligomericmono- or poly-hydroxy and amino compounds, the reactive performanceadditive functional groups can be partially replaced with reactivecompounds that do not possess performance additive functions. The latterinclude, for example, acid chlorides, such as acetyl chloride,2-ethylhexanoyl chloride, pivaloyl chloride dodecanoyl chloride,neodecanoyl chloride, benozyl chloride, 4-methylbenzoyl chloride,2-naphthoyl chloride, acryloxy chloride, undecylenoyl chloride and ethyl2-chlorocarbonyl benzoate; chloroformates, such as methyl chloroformate,isopropyl chloroformate, phenyl chloroformate, 2-ethylhexylchloroformate, dodecyl chloroformate, 2-phenoxyethyl chloroformate andallyl chloroformate; isocyanates, such as methyl isocyanate, propylisocyanate, 2-(4-isopropenylphenyl)-2-propyl isocyanate and phenylisocyanate; carbamoyl chlorides, such as N,N-dimethylcarbamoyl chloride;sulfonyl chlorides, such as methylsulfonyl chloride, phenylsulfonylchloride and p-tolylsulfonyl chloride; perfluoro carboxylic acidchlorides, such as trifluoroacetyl chloride and perfluoroheptanoylchloride; diketene; ketene; 2,2,6-trimethyl-4H-1,3-dioxin-4-one (adiketene precursor); and acid anhydrides, such as acetic anhydride,propionic anhydride, succinic anhydride, decenylsuccinic anhydride,itaconic anhydride, glutaric anhydride, phthalic anhydride,4-methylphthalic anhydride, 4-nitrophthalic anhydride, trimelliticanhydride, pyromellitic dianhydride, benzophenone dianhydride,tetrahydrophthalic anhydride, hexahydrophthalic anhydride.

In general, cyclic carboxylic anhydrides, such as succinic anhydride,glutaric anhydride, phthalic anhydride, hexahydrophthalic anhydride, andothers, react with hydroxy compounds to form 2-, 3- or4-carboxy-carboxylates which are usually unstable thermally. At elevatedtemperatures they decompose to produce the starting reactants, i.e., thealcohol and the cyclic carboxylic anhydride. In order to prevent thisfrom happening, the 2-, 3- or 4-carboxy-carboxylate is furtheresterified with alcohols or with epoxides to form the correspondingalkyl alkyl' dicarboxylate or alkyl 2-hydroxyalkyl' dicarboxylate.Epoxides useful in this respect include, for example, ethylene oxide,propylene oxide, 1,2-butylene oxide, styrene oxide, cyclohexene oxideand epichlorohydrin.

Oligomeric mono- or ply-hydroxy and amino compounds which are reactivewith AO's, UV stabilizers, light stabilizers and flame retardantspossessing reactive acid halide, acid anhydride or chloroformate groupsinclude, for example, oligomeric bisphenol A polycarbonates,tetrabromobisphenol A polycarbonates and copolycarbonates possessinghydroxy and groups, oligomeric aliphatic polycarbonates possessinghydroxy end groups (such as PPG's Duracarb® polycarbonate oligomers);oligomeric aliphatic and aromatic polyesters possessing hydroxy endgroups (such as Witco's Fomrez® aliphatic polyester oligomers and KingIndustries' K-Flex® oligomers); oligomeric polycaprolactones possessinghydroxy end groups (such as Union Carbide's TONE® oligomers); oligomericpolyethers possessing hydroxyl or amino end groups (such as UnionCarbide's Carbowax® and Niax® oligomers, PRC's Permapol®polyetherpolysulfide diol oligomers, and Texaco's Jerramine® aminoterminated polyether oligomers); oligomeric partially hydrolyzedpoly(vinyl acetates); oligomeric poly(styrene-co-allyl alcohol); andoligomeric polybutadienes possessing hydroxy end groups.

The above mono- and poly-hydroxy and amino oligomers can be converted tochloroformates or carbamoyl chlorides, e.g., mono- orpoly-chloroformates or mono- and poly-carbamoyl chlorides of oligomericmono- or poly-hydroxy and amino comounds, and subsequently reacted withhydroxy-substituted AO's, UV stabilizers, light stabilizers and flameretardants, in the presence of appropriate basic compounds to producethe compositions of the present invention.

As indicated above, generally, either the performance additives or theoligomers with which they are reacted can contain various correspondingreactive substituents. In general, the reaction conditions for theperformance additives with the oligomeric comounds involving thecorresponding reactive substituents set forth above are such that themole ratio of hydroxyl (or amino) groups to chloroformate (or carbamoylchloride) groups is between about 3.0 and about 0.5, preferably betweenabout 1.25 and about 0.75, and most preferably between about 1.1 andabout 0.9. The reaction temperature is between about -50° C. and about150° C., preferably between about -10° C. and about 75° C. and mostpreferably between about 0° C. and about 50° C.

A solvent may or may not be needed, depending upon the reactants used.If a solvent is used, the solvent should be capable of dissolving thereactants without reacting with them. Examples of suitable solvents arehydrocarbon solvents, such as hexane and toluene; ether solvents, suchas tetrahydrofuran, methyl t-butyl ether and glyme; chlorinatedhydrocarbon solvents, such as methylene chloride, chloroform andchlorobenzene; and ester solvents, such as ethylacetate and butylacetate.

A base may also be used to neutralize hydrogen chloride given off duringthe course of the reaction. Examples of suitable bases are sodiumhydroxide, potassium hydroxide, sodium (or potassium) carbonate orbicarbonate, triethyl amine, tributyl amine and pyridine. The mole ratioof base to chloroformate is between about 1.0 and about 5.0. Inaddition, a nucleophilic catalyst may be used to accelerate the reactionrate. Such catalysts are known in the literature, with an example beingp-N,N-dimethylaminopyridine. The mole ratio of catalyst to chloroformateis between about 0.001 and about 0.1.

As indicated above, the experiments involving fire retardant oligomericperformance additives led to the discovery that the compounds ofStructure C, generally referred to herein as "sulfobenzoic acidcompounds and derivatives," themselves provide flame retardantproperties when reacted with or blended with aromatic polycarbonateresin compositions. Some of the compounds of Structure C are knowncompounds, however, none are known to have been used as fire retardantsfor aromatic polycarbonates. Moreover, the compounds in which R10 has astructure corresponding to UV stabilizing structures (1) through (4) arebelieved to be novel compounds themselves and provide combined UVstabilizing and flame retardant properties to aromatic polycarbonates.

To produce a non-fugitive fire retardant polymer or co-polymer includingan aromatic polycarbonate in which the fire retardant properties areprovided by the sulfobenzoic acid compounds and derivatives of thepresent invention, about 0.01% to about 10%, based on the weight of thepolymer or co-polymer, of the sulfobenzoic acid compound or derivativeis blended with the polymer or co-polymer.

To make oligomeric additive comounds including the sulfobenzoic acidcomounds and derivatives as the performance additives, the generalreaction conditions are as follows: The oligomer is dissolved in asuitable solvent, such as dry toluene, methylene chloride, ethyl acetateor butyl acetate, and an anhydrous base such as sodium (or potassium)carbonate or bicarbonate is added. Then the sulfobenzoic acid cyclicanhydride compound is added to the well stirred suspension. The reactionmixture is heated until the evolution of carbon dioxide has ceased. Theunreacted base can either be removed by filtration or by washing withaqueous acid until a pH 5-7 has been obtained. The mole ratio of base tosulfobenzoic acid cyclic anhydride is between about 1 and about 5, andpreferably between about 1.5 and about 3.0. the mole ratio of hydroxylgroups (on the oligomer) to sulfobenzoic acid cyclic anyhydride isbetween about 10 and about 0.8, and preferably between about 5 and about0.9, and the reaction temperature is between about 25° C. and about 150°C.

The following illustrative, non-limiting examples are included for thepurpose of further describing and explaining the preparation and use ofthe oligomeric performance additives of the present invention. Examples1 through 26 illustrate the preparation of various types of oligomericperformance additives according to the present invention.

EXAMPLE 1 Endcapping TONE® 260 with 2-Sulfobenzoic Acid CyclicAnhydride, Sodium Hydrogen Carbonate as the Base (Compound I-1)

A three-neck round-bottom flask, fitted with a nitrogen inlet line, athermometer, and a Friedrich condenser possessing a mineral oil bubbler,was charged with 50.0 g (32.9 m.e.q.) of TONE® 260 (an oligomericpolycarpolactone based diol, having a molecular weight of ca. 3000 basedon a hydroxyl content of 1.12%, manufactured by Union CarbideCorporation) and 150 mL of dry toluene. After the TONE® 260 dissolved, aclear, colorless solution was obtained. Anhydrous, powdered sodiumhydrogen carbonate (6.0 g; 71.4 mmoles) was added, and the magneticallystirred suspension was purged with dry nitrogen for 10 minutes. Next,6.84 g (35.3 mmoles) of technical grad 2sulfobenzoic acid cyclicanhydride were quickly added in one portion. The nitrogen flow was shutoff, and the stirred mixture was gradually warmed in an oil bath to 100°C. over approximately 120 minutes during which time carbon dioxideevolution was observed. After the evolution of carbon dioxide ceased(ca. 2-3 hours), the reaction mixture was cooled to room temperature andpoured into 1.0 L of fresh toluene. The resulting toluene mixture wasthen suction filtered through a 350 mL coarse fritted glass filterfunnel to which about 15 g of Celite 503 filter aid had been added. Thespent filter cake was washed with fresh toluene, and the combinedtoluene filtrates were stripped of volatiles using a water aspirator anda rotary evaporator. A viscous oil was obtained which still containedtoluene. The residual toluene was removed by heating the oil, underapproximately 1.0 mm vacuum, to 110° C. for 15 minutes.

Upon cooling, 59.3 g (theory, 56.8 g) of an off white waxy solidmaterial was obtained. The sulfur analysis expected was 1.86% and thesulfur analysis found was 1.8%. An infrared (IR) spectrum of the productshowed the expected absorption bands at 1026 cm⁻¹ for the sulfonic acidsalt group and at 660 cm⁻¹ and 619 cm⁻¹ for the aromatic group. Thesebands were not present in the starting TONE® 260. Based on the method ofpreparation and analyses, the product formed in this reaction, I-1, wasa disodium salt of bis(2-sulfobenzoyloxy) endcapped TONE® 260, adisodium disulfonic acid salt.

EXAMPLE 2 Endcapping TONE® 260 with 2-Sulfobenzoic Acid CyclicAnhydride, Potassium Carbonate as the Base (Compound I-2)

100.2 g (66.0 m.e.q.) of TONE® 260, 13.4 g (69.1 mmoles) of technicalgrade 2-sulfobenzoic cyclic anhydride, and 18.8 g (136.0 mmoles) ofpotassium carbonate were allowed to react in 500 mL of dry toluene usinga method similar to the one employed in Example 1. The reaction mixturewas diluted with 1.5 L of fresh toluene, and was suction filteredthrough a bed of Celite 503 filter aid. After removal of the volatilesas in example 1, 112.7 g (theory, 114.9 g) of a light yellow waxy solidwere obtained. The sulfur analysis expected was 1.84% and the sulfuranalysis found was 2.0%. The potassium analysis expected was 2.25% andthe potassium analysis found was 2.5%. Based on the method ofpreparation and analyses, the product formed in this reaction, I-2, wasa dipotassium salt of bis(2-sulfobenzoyloxy) endcapped TONE® 260, adipotassium disulfonic acid salt.

EXAMPLE 3 Endcapping TONE® 260 with 2-Sulfobenzoic Acid CyclicAnhydride, Potassium Hydrogen Carbonate as the Base (Compound I-2)

50.0 g (32.9 m.e.q.) of TONE® 260, 6.9 g (35.6 mmoles) of technicalgrade 2-sulfobenzoic cyclic anhydride, and 6.0 g (60.0 mmoles) ofanhydrous potassium hydrogen carbonate were allowed to react in 250 mLof dry toluene using a method similar to the one employed in Example 1.The reaction mixture was diluted with 600 mL of fresh toluene, and wassuction filtered twice through a bed of Celite 503 filter aid. Afterremoval of the volatiles as in Example 1, 55.2 g (theory, 57.3 g) of alight yellow waxy solid were obtained. The sulfur analysis expected was1.84% and the sulfur analysis found was 1.6%. An infrared (IR) spectrumof the product showed the expected absorption bands at 1024 cm⁻¹ for thesulfonic acid salt group and at 660 cm⁻¹ and 619 cm⁻¹ for the aromaticgroup. These bands were not present in the starting TONE® 260. Based onthe method of preparation and analyses, the product formed in thisreaction, I-2, was a dipotassium salt of bis(2-sulfobenzoyloxy)endcapped TONE® , a dipotassium disulfonic acid salt.

EXAMPLE 4 Endcapping TONE® 260 with 2-Sulfobenzoic Acid CyclicAnhydride, Sodium Carbonate as the Base (Compound I-1)

100.2 g (65.9 m.e.q.) of TONE® 260, 13.4 g(69.3 mmoles) of technicalgrade 2-sulfobenzoic cyclic anhydride, and 14.4 g (136.0 mmoles) ofanhydrous sodium carbonate were allowed to react in 500 mL of drytoluene using a method similar to the one employed in Example 1, exceptthat the reaction mixture was heated to 100° C. over 1 hour instead of 2hours, and that the total reaction time was 2 hours rather than 4-5hours. The reaction mixture was diluted with 1.5 L of fresh toluene, andwas suction filtered through a bed of Celite 503 filter aid. Afterremoval of the volatiles as in Example 1, 112.7 g (theory, 113.6 g) of ayellow waxy solid was obtained. The sulfur analysis expected was 1.86%and the sulfur analysis found was 1.7%. The sodium analysis found was1.0%. An infrared (IR) spectrum of the product showed the expectedabsorption bands at 1026 cm⁻¹ for the sulfonic acid salt group and at660 cm⁻¹ and 619 cm⁻¹ for the aromatic group. These bands were notpresent in the starting TONE® 260. Based on the method of preparationand analyses, the product formed in this reaction, I-1, was a disodiumsalt of bis(2-sulfobenzoyloxy) endcapped TONE® 260, a disodiumdisulfonic acid salt.

EXAMPLE 5 Endcapping A Monohydroxy-Terminated Polycaprolactone Oligomerwith 2-Sulfobenzoic Acid Cyclic Anhydride, Sodium Hydrogen Carbonate asthe Base (Compound I-3)

A mixture containing 100.0 g (876 mmoles) of caprolactone, 11.6 g (100.0mmoles) of n-heptanol, and 0.01 g of potassium carbonate was heatedunder nitrogen to 175° C. for 44 hours. The resultant waxy solid(yield=111 g) assayed for 0.6% residual n-heptanol, 0.3% residualcaprolactone, and the desired polycaprolactone oligomer containing 1.4%by weight of hydroxyl. The latter indicated that the oligomer had about9 caprolactone repeat units and that the molecular weight of theoligomer was about 1200.

Next, 50.0 g (41.2 mmoles) of the above oligomer, 8.8 g (45.4 mmoles) oftechnical grade 2-sulfobenzoic acid anhydride, and 10.4 g (124.0 mmoles)of anhydrous sodium hydrogen carbonate were allowed to react in 300 mLof dry toluene using a method similar to that employed in Example 1. Thereaction mixture was diluted with 300 mL of fresh toluene and wassuction filtered through a bed of Celite 503 filter aid. After removalof volatiles as in Example 1, 56.6 g (theory, 58.5 g) of a tan wax wasobtained. The sulfur analysis expected was 2.26% and the sulfur analysisfound was 1.7%. Based on the method of preparation and analyses, theproduct formed in this reaction, I-3, was a monosodium salt ofmono-(2-sulfobenzoyloxy)polycaprolactone oligomer.

EXAMPLE 6 Partial Endcapping of Duracarb® 120 with 2-Sulfobenzoic AcidCyclic Anhydride, Potassium Hydrogen Carbonate as the Base (CompoundsI-4a and I-4b)

In this example 50.0 g (122.9 m.e.q.) of Duracarb® 120 (an aliphaticpolycarbonate oligomeric diol, having a molecular weight of about 850based on a hydroxyl content of 4.18 weight %, manufactured by PPGIndustries), 12.0 g (61.9 mmoles) of technical grade 2-sulfobenzoiccyclic anhydride, 12.0 g (1220.0 mmoles) of anhydrous potassiumcarbonate, and 12.0 g of crushed 4A molecular sieves were allowed toreact in 300 mL of dry toluene using a method similar to the oneemployed in Example 1, except that the reaction mixture was heated to100° C. over 1 hour instead of 2 hours and that the total reaction timewas 2 hours rather than 4-5 hours. The reaction mixture was diluted with1.0 L of fresh toluene, and was suction filtered twice through a bed ofCelite 503 filter aid. A small amount of toluene insoluble, gel-likematerial was recovered from the bottom of the filter flask after thetoluene solution was removed for stripping. After drying under vacuum,1.2 g of toluene insoluble solid were obtained. This was thought to bethe di-endcapped oligomer.

After removal of the volatiles as in Example 1, 48.8 g (theory, 63.7 g)of a light yellow waxy solid was obtained from the toluene solution. Thesulfur analysis expected for the toluene soluble fraction was 3.1%(mono-endcapped) and the sulfur analysis found was 2.6%. The sulfuranalysis expected for the toluene insoluble soluble fraction was 6.2%(di-endcapped) and the sulfur analysis found was 5.1%. An infrared (IR)spectrum of the toluene soluble product showed the expected absorptionbands at 1023 cm⁻¹ for the sulfonic acid salt group and at 660 cm⁻¹ and619 cm⁻¹ for the aromatic group. These bands were not present in thestarting Duracarb® 120. Based on method of preparation and analyses, theproducts formed in this reaction were as follows: The toluene solubleproduct, I-4a, was the mono-endcapped product (the monopotassium salt ofmono(2-sulfobenzoyloxy) endcapped Duracarb® 120) and the tolueneinsoluble product, I-4b, was the di-endcapped product (the dipotassiumsalt of bis(2-sulfobenzoyloxy) endcapped Duracarb® 120).

EXAMPLE 7 Endcapping of Duracarb® 120 with 2-Sulfobenzoic Acid CyclicAnhydride and Tetrabromophthalic Anhydride, Followed by Reaction withEpichlorohydrin (Compounds I-5a, I-5b and I-5c)

In this example 50.0 g (122.9 m.e.q.) of Duracarb® 120, 8.0 g (80.0mmoles) of anhydrous sodium carbonate, and 8.0 g (41.3 mmoles) ofcrushed 4A molecular sieves were allowed to react in 300 mL of drytoluene with 8.0 g of technical grad 2-sulfobenzoic cyclic anhydride,using a method similar to the one employed in Example 1, except that thereaction mixture was heated to 110° C. over 1 hour instead of 2 hours,and that the total reaction time was 2 hours rather than 4-5 hours. Thecooled reaction mixture was then suction filtered through a bed ofCelite 503 filter aid and the filter cake was washed with a small amountof fresh toluene. The combined toluene solutions were then added to anErlenmeyer flask, whereupon 38.8 g (82.0 mmoles) of tetrabromophthalicanhydride (TBPA) and 1.5 g (15.3 mmoles) of potassium acetate wereadded. A Friedrich condenser was attached to the flask and themagnetically stirred suspension was warmed to 100° C. over a period of30 minutes. At this point, all of the TBPA was in solution. Then 11.4 g(123.0 mmoles) of epichlorohydrin were added and the solution wasstirred for an hour at 100° C. The cooled solution was filtered througha bed of Celite 503 filter aid and the filter cake was washed with asmall amount of fresh toluene. The toluene solutions were then combined.

After removal of the volatiles as in Example 1, 99.2 g (theory, 104.7 g)of a faintly yellow waxy solid were obtained. The sulfur analysisexpected was 1.25% and the sulfur analysis found was 1.2%. The bromineanalysis expected was 25.0% and the bromine analysis found was 24.7%.Hence, the product obtained was the desired product containing2-(potassium sulfo)benzoyloxy end groups and2-(chlorohydroxypropoxycarbonyl)-3,4,5,6-tetrabromobenzoyloxy end groupsin an equivalent ratio of about 1 to 2. An infrared (IR) spectrum of thetoluene soluble product showed the expected absorption bands at 1022cm⁻¹ for the sulfonic acid salt group and at 660 cm⁻¹ and 618 cm⁻¹ forthe aromatic group. These bands were not present in the startingDuracarb® 120. Based on method of preparation and analyses, the productformed in this reaction was a mixture of abis(2-chlorohydroxypropoxycarbonyl) endcapped Duracarb® 120 oligomer(I-5a), a disodium salt of a bis(2-sulfobenzoyloxy) endcapped Duracarb®120 oligomer (I-5b), and a monosodium salt of amono(2-chlorohydroxypropoxycarbonyl)3,4,5,6-tetrabromobenzoyloxy,mono(2-sulfobenzoyloxy) endcapped Duracarb® 120 oligomer (I-5c).

EXAMPLE 8 Endcapping Fomrez® 53 with 2-Sulfobenzoic Acid CyclicAnhydride, Potassium Hydrogen Carbonate as the Base (Compound I-6)

50.0 g (46.5 m.e.q.) of Fomrez® 53 (an aliphatic branded glycol adipatepolyester, having a molecular weight of about 2100 based on a hydroxylcontent of 1.58 weight %, manufactured by Witco Chemical Corp.), 10.0 g(100.0 mmoles) of anhydrous potassium hydrogen carbonate and 300 mL ofdry toluene were magnetically stirred and simultaneously purged withnitrogen at room temperature for about 10 minutes. Then 9.2 g (47.5mmoles) of technical grade 2-sulfobenzoic cyclic anhydride were added tothe suspension in one portion. A Friedrich condenser with an attachedmineral oil bubbler was placed on top of the flask, and the mixture washeated to reflux for about 2 hours. After cooling, the reaction mixturewas suction filtered through a bed of Celite 503 filter aid and thefilter cake was washed with fresh toluene. The toluene solutions werecombined.

After removal of the volatiles as in Example 1, 66.3 g (theory, 60.3 g)of a viscous light yellow oil was obtained. The sulfur analysis expectedwas 2.47% and the sulfur analysis found was 2.1%. The above theory yieldand the below theory sulfur analysis indicated that the product wascontaminated with solvent. An infrared (IR) spectrum of the productshowed the expected absorption bands at 1026 cm⁻¹ for the sulfonic acidsalt group and at 660 cm⁻¹ and 617 cm⁻¹ for the aromatic group. Thesebands were not present in the starting Fomrez® 53. Based on the methodof preparation and analyses, the product formed in this reaction, I-6,was a dipotassium salt of a bis(2-sulfobenzoyloxy) endcapped Fomrez® 53oligomer, a dipotassium salt of a disulfonic acid.

EXAMPLE 9 Endcapping TONE® 260 with 3,5-Di-t-butyl-4-hydroxybenzoylChloride (Compound I-7)

A solution of 20.0 g (13.2 m.e.q) of TONE® 260 and 2.0 g (25.3 mmoles)of pyridine in 75 mL of methylene chloride was purged with nitrogen.This solution was cooled in a slat-ice bath and to it was added (over aperiod of 30 minutes) a solution consisting of 3.79 g (14.1 mmoles) of3,5-di-t-butyl-4-hydroxybenzoyl chloride in 25 mL of methylene chloride.The reaction mixture was allowed to warm to room temperature over aperiod of 60 minutes and was then warmed to reflux for 60 minutes. Aftercooling, the mixture was washed once with 10% aqueous HC1 solution,twice with water and once with 2% sodium hydrogen carbonate solution.The solution was then dried over 5% by weight of anhydrous magnesiumsulfate, and, after separation of the spent desiccant by filtration, thesolvent was removed from the solution in vacuo.

The product was 21.8 g (theory, 23.1 g) of a waxy white solid. Theproduct was contaminated with 0.5% 3,5-di-t-butyl-4-hydroxybenzoic acidaccording to liquid chromatographic (LC) analysis. An infrared (IR)spectrum of the product showed the expected absorption bands at 1461cm⁻¹ and 1435 cm⁻¹ for the aromatic group which were not present in thestarting TONE® 260 oligomer. Based on the method of preparation andanalyses, the product formed in this reaction, I-7, was abis(3,5-di-t-butyl-4-hydroxybenzoyloxy) endcapped TONE® 260 oligomer.

EXAMPLE 10 Endcapping of Other Diol Oligomers with3,5-Di-t-butyl-4-hydroxybenzoyl Chloride (Compounds I-8 and I-9)

Employing the procedure used in Example 9, two other oligomeric diols,Permapol® P-900 (an oligomeric polyether-polysulfide diol, having amolecular weight of about 500 based on a hydroxyl content of 6.91 weight%, manufactured by PRC Corp.) and K-Flex® 148 (an aliphatic oligomericester diol, having a molecular weight of about 500 based on a hydroxylcontent of 7.01 weight %, manufactured by King Industries), wereendcapped with 3,5-t-butyl-4-hydroxybenzoyl chloride (AO BCl). The tablebelow summarizes the quantities of reactants and the yield informationabout each oligomer.

    ______________________________________                                                          Product Yield                                               Reactants Quantity, g   Theory, g Actual, g                                   ______________________________________                                        Permapol P-900                                                                          20.0   (81.3 meq.)                                                  AO BCl    21.8   (81.3 mmol.)                                                                             38.8    37.2.sup.1 (I-8)                          Pyridine  7.9    (100.0 mmol.)                                                K-Flex 148                                                                              23.8   (98.1 meq.)                                                  AO BCl    27.1   (101.0 mmol.)                                                                            46.6    41.7.sup.2 (I-9)                          Pyridine  16.0   (202.0 mmol.)                                                ______________________________________                                         .sup.1 A light yellow oil.                                                    .sup.2 A straw colored viscous oil, IR spectrum showed carbonyl bands at      1715 cm.sup.-1 and 1780 cm.sup.-1 whereas KFlex ® 148 showed a single     carbonyl band at 1770 cm .sup.-1.                                        

Based on the method of preparation and analyses, I-8 was abis(3,5-di-t-butyl-4-hydroxybenzoyloxy) endcapped Permapol® P-900oligomer. Based on the method of preparation and analyses, I-9 was abis(3,5-di-t-butyl-4-hydroxybenzoyloxy) encapped K-Flex® 148 oligomer.

EXAMPLE 11 Encapping TONE® 260 with3-(3,5-Di-t-butyl-4-hydroxyphenyl)propionyl chloride (Compound (I-10)

A solution of 21.2 g (14.0 m.e.q.) of TONE® 260 and 1.8 g (22.8 mmoles)of pyridine in 50 mL of methylene chloride was purged with nitrogen.This solution was cooled in a salt-ice bath and to it was added (over aperiod of 60 minutes) a solution consisting of 4.5 g (15.2 mmoles) of3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl chloride in 25 mL ofmethylene chloride. The reaction was completed and the product wasworked-up as in Example 9. Obtained were 25.0 g (theory, 24.8 g) of alight yellow wax which was contaminated with 1.1%3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid according to LCanalysis. An infrared (IR) spectrum of the product showed the expectedabsorption bands at 1471 cm⁻¹ and 1436 cm⁻¹ for the aromatic group whichwere not present in the starting TONE® 260 oligomer. Based on the methodof preparation and analyses, the product formed in this reaction, I-10,was a bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy) endcappedTONE® 260 oligomer.

EXAMPLE 12 Endcapping of Other Diol Oligomers with3-(3,5-Di-t-butyl-4-hydroxyphenyl)propionyl Chloride (Compounds I-11 andI-12)

Employing the procedure used in Example 11 two other oligomeric diols,Permapol® P-900 and K-Flex® 148, were endcapped with3-(3,5-t-butyl-4-hydroxyphenyl)propionyl chloride (AO PCl). The tablebelow summarizes the quantities of reactants used and the yieldinformation about each oligomer.

    ______________________________________                                                          Product Yield                                               Reactants Quantity, g   Theory, g Actual, g                                   ______________________________________                                        Permapol P-900                                                                          25.0   (101.6 meq.)                                                 AO PCl    29.5   (99.4 mmol.)                                                                             50.9    45.7.sup.1 (I-11)                         Pyridine  16.6   (210.0 mmol.)                                                K-Flex 148                                                                              23.8   (98.4 meq.)                                                  AO PCl    29.5   (99.4 mmol.)                                                                             49.7    45.2.sup.2 (I-12)                         Pyridine  7.9    (100.0 mmol.)                                                ______________________________________                                         .sup.1 A straw yellow oil, IR spectrum showed ester carbonyl bands at 173     cm.sup.-1 and 1750 cm.sup.-1, bands absent in starting Permapol ®         P900.                                                                         .sup.2 A straw colored viscous oil, IR spectrum showed ester carbonyl         bands and a very sharp hindered phenol band at 3650 cm.sup.-1 . The latte     band was absent in KFlex ® 148.                                      

Based on the method of preparation and analyses, I-11 was abis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy) endcapped Permapol®P-900 oligomer.

Based on the method of preparation and analyses, I-12 was abis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy) endcapped K-Flex®148 oligomer.

EXAMPLE 13 Endcapping TONE® 260 with 2-(4-Benzoyl-3-hydroxyphenoxy)ethylChloroformate (Compound (I-13)

2-(4-Benzoyl-3-hydroxyphenoxy)ethyl chloroformate was prepared byinitially reacting 2,4-dihydroxybenzophenone with ethylene oxide andsubsequently converting the resulting2-hydroxy-4-(2-hydroxy-ethoxy)benzophenone to the desired chloroformatevia treatment with excess phosgene. Employing the procedure used inExample 11, 25.0 g (16.5 m.e.q.) of TONE® 260 and 6.0 g (17.8 mmoles) of2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate (95.4%) were reactedin the presence of 1.4 g (17.8 mmoles) of pyridine and 150 mL ofmethylene chloride. The reaction was completed and the product wasworked up as in Example 9.

28.4 g (theory, 30.1 g) of a light yellow waxy solid were obtained. Highperformance LC (UV detector) indicated the presence of 2.5% of residual2-hydroxy-4-(2-hydroxyethoxy)benzophenone in the product. There was alsoa very large increase in the UV absorption for the LC peak thatcorresponded to that of TONE® 260. This demonstrated that the UVabsorbing moiety was indeed attached to the TONE® 260 oligomer and thatthe desired product was formed. Based on the method or preparation andanalyses, the product formed in this reaction, I-13, was abis(2-(4-benzoyl-3-hydroxyphenoxy)-ethoxycarbonyloxy) endcapped TONE®260 oligomer.

EXAMPLE 14 Endcapping TONE® 260 with Diethyl Chlorophosphite (CompoundI-14)

Employing the procedure used in Example 11, 50.0 g (32.9 m.e.q.) ofTONE® 260 and 6.2 g (38.8 mmoles) of 98% diethyl chlorophosphite werereacted in the presence of 5.0 g (49.4 mmoles) of triethylamine and 200mL of methylene chloride. After the usual work-up, 50.1 g (theory, 54.0g) of a white waxy solid was obtained. The phosphorous analysis expectedfor the desired product was 2.02%; that found was 1.89%. An infrared(IR) spectrum of the product showed the expected absorption bands at1038 cm⁻¹ and 778 cm⁻¹ which show the presence of an aliphatic P--O--Cbond in the product. Based on the method of preparation and anlayses,the product formed in this reaction, I- 14, was abis(diethoxyphosphinoxy) endcapped TONE® 260 oligomer.

EXAMPLE 15 Endcapping TONE® 220 with 3,3-Diphenyl-2-cyano-2-propenoylChloride (Compound I-15)

Employing the procedure used in Example 11, 10.0 g (19.8 m.e.q.) ofTONE® 220 (an oligomeric polycaprolactone diol, having a molecularweight of ca. 1000 based on a hydroxyl content of 3.37%, manufactured byUnion Carbide Corporation) and 5.34 g (19.8 mmoles) of 99.2%3,3-diphenyl-2-cyano-2-propenoyl chloride were reacted in the presenceof 2.0 g (25.3 mmoles) of pyridine and 50 mL of dry methylene chloride.12.9 g (theory, 14.6 g) of an amber waxy solid were obtained. Highperformance LC (UV detector) showed a very large increase in the UVabsorption for the LC peak that corresponded to that of TONE® 220. Thisdemonstrated that the UV absorbing moiety was indeed attached to theTONE® 220 oligomer and that the desired product was formed. The LCanalysis also showed that the product was contaminated with less than0.1 weight % 3,3-diphenyl-2-cyano-2-propenoic acid. An infrared (IR)spectrum of the product showed the expected absorption band at 2220 cm⁻¹for the cyano group in the product. Based on the method of preparationand analyses, the product formed in this reaction, I-15, was abis(3,3-diphenyl-2-cyano-2-propenoyloxy) endcapped TONE® 220 oligomer.

EXAMPLE 16 Endcapping TONE® 260 with 2-(4-Benzoyl-3-hydroxyphenoxy)ethylChloroformate and 3,5-Di-t-butyl-4-hydroxybenzoyl Chloride (CompoundsI-16a, I-16b and I-16c)

Employing the procedure used in Example 11, 50.0 g (32.9 m.e.q.) ofTONE® 260, 4.74 g (17.6 mmoles) of 3,5-di-t-butyl-4-hydroxybenzoylchloride and 5.88 g (17.6 mmoles) of 96.1%2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate were reacted in thepresence of 3.1 g (39.2 mmoles) of pyridine and 300 mL of methylenechloride. 55.6 g (theory, 58.5 g) of a light yellow waxy solid wereobtained. High performance LC (UV detector) indicated the presence of2.1% of residual 2-hydroxy-4-(2-hydroxyethoxy)benzophenone and less than0.1% residual, 3,5-di-t-butyl-4-hydroxybenzoic acid in the product. Anultraviolet (UV) spectrum of the product showed lambda max. absorptionbands at 224 nm, 254, nm, 284 nm, and 328 nm. Based on the method ofpreparation and analyses, the product formed in this reaction, I-16, wasa mixture of a bis(2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonyloxy)endcapped TONE® 260 oligomer (I-16a), abis(3,5-di-t-butyl-4-hdyroxybenzoyloxy) endcapped TONE® 260 oligomer(I-16b) and a mono(3,5-di-t-butyl-4-hydroxybenzoyloxy),mono(2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonyloxy) endcapped TONE®260 oligomer (I-16c).

EXAMPLE 17 Endcapping a Tetrabromobisphenol A Polycarbonate (PC) with2-(4-Benzoyl-3-hydroxyphenoxy)ethyl Chloroformate (Compound I-17)

A 500 mL 4-necked flask was fitted with a mechanical stirrer, twoaddition funnels, and a Claisen adapter to which were connected athermometer and a Dry Ice-filled Dewar condenser. A small Dry Ice-filledDewar condenser was also attached to the addition funnel that held theliquid phosgene.

Next, 32.6 g (60.0 mmoles) of tetrabromobisphenol A, 0.2 g(0.6 mmole) oftetrabutylammonium hydrogen sulfate (phase transfer catalyst), 53.2 g(60.0 mmoles) of 4.5% aqueous sodium hydroxide solution, and 100 mL ofmethylene chloride were added. The mixture was stirred and 5.02 g (15.0mmoles) of 96% 2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate in 30mL of methylene chloride were added dropwise over 10 minutes. After thereaction mixture was stirred an additional 5 minutes, 8.3 mL (ca. 119.0mmoles) of liquid phosgene and 12.0 g (150.0 mmoles) of 50% sodiumhydroxide were added dropwise over 20 minutes. The reaction mixture wascooled as was necessary in order to hold the temperature between 20° and25° C. Once the addition of phosgene was completed, 0.5 mL (ca. 4.9mmoles) of triethylamine was added. The reaction mixture was stirredanother 30 minutes. At the end of this time the pH of the aqueous phasewas 12-14 according to pH paper. The phases were separated. Themethylene chloride phase was washed once with dilute aqueous HClsolution and once with water. It was then added dropwise to 1.0 L ofvigorously stirred methanol.

The resultant precipitate was filtered, washed with fresh methanol anddried in a vacuum oven to yield 30.1 g (theory, 38.3 g) of white powder.Analysis by high performance LC indicated the presence of less than 0.1weight % residual 2-hydroxy-4-(2-hydroxyethoxy)benzophenone in theproduct. Analysis by ultraviolet (UV) spectroscopy showed that theproduct contained about .4 weight % of attached2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonyloxy) UV absorbing groups.Based on the method of preparation and analyses, the product formed inthis reaction, I-17, was abis(2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonyloxy) endcappedtetrabromobisphenol A polycarbonate (PC) oligomer.

EXAMPLE 18 Endcapping a Bisphenol A Polycarbonate (PC) with2-(4-Benzoyl-3-hydroxyphenoxy)ethyl Chloroformate (Compound I-18)

A 2.0 L 3-necked flask was fitted with a mechanical stirrer, a nitrogeninlet line, and a Claisen adapter to which was connected a DryIce-filled Dewar condenser and a thermometer. The nitrogen line wasconnected to a 100 mL flask to which was attached an addition funneltopped with a small Dry Ice-filled Dewar condenser. In this way ameasured amount of liquid phosgene was added dropwise to the 100 mLflask where it vaporized and was swept by the nitrogen flow into the 2.0L flask.

300 mL of dry methylene chloride, 57.1 g (250 mmoles) of bisphenol A,160 g (2.022 moles) of pyridine, and 0.8 g (5.6 mmoles) of4-(N,N-dimethylamino)pyridine (a nucleophilic catalyst) were added tothe 2.0 L flask. The stirred solution was purged with nitrogen for 10minutes before 8.4 g (25.0 mmoles) of 95.4%2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate in 25 mL of methylenechloride was added in one portion. After the reaction mixture wasstirred for 90 minutes at 25°-30° C., an additional 300 mL of drymethylene chloride were added. Then 50.0 mL (ca. 723 mmoles) of liquidphosgene were added as a gas through the nitrogen line below the surfaceof the liquid, over a period of 30 minutes at 25°-30° C. After stirringthe mixture for an additional 60 minutes, 25 mL of water were carefullyadded to destroy the excess phosgene. An additional 125 mL of water wereadded and the mixture was stirred for 30 minutes. The reaction mixturewas then diluted with about 600 mL of methylene chloride and themethylene chloride phase was washed with 600 mL of 5% aqueous HCl, thenwith water. The methylene chloride solution was then added to 2.0 L ofvigorously stirred methanol.

The resulting precipitate was separated by filtration and dried in avacuum oven to yield 45.1 g (theory, 70.7 g) of light yellow powder.Analysis by high performance LC indicated that there was less than 0.1%of residual 2-hydroxy-4-(2-hydroxyethoxy)benzophenone in the product.The resulting endcapped bisphenol A PC had a stronger UV absorptionaccording to LC than a similar bisphenol A PC endcapped with a phenol.Analysis by ultraviolet (UV) spectroscopy showed that the productcontained about 2.5 weight % of attached2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonyloxy) UV absorbing groups.Based on the method of preparation and analyses, the product formed inthis reaction, I-18, was abis(2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonyloxy) endcapped bisphenolA polycarbonate (PC) oligomer.

EXAMPLE 19 Endcapping of Jeffamine® M-600 with2-(4-Benzoyl-2-hydroxyphenoxy)ethyl Chloroformate (Compound I-19)

A solution of 11.8 g (35.0 mmoles) of 95.4%2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate in 50 mL of drymethylene chloride was added at room temperature to 20.0 g (35.0 mmoles)of Jeffamine® M-600 (a monoamino oligomeric polyether with a molecularweight of about 600 based on 2.80 weight % amino groups, produced byTexaco, Inc.) in 75 mL of dry methylene chloride. The resulting solutionwas stirred for 12 hours at room temperature. The reaction mixture wasthen washed four times with 5% aqueous sodium hydroxide solution andonce with saturated sodium hydrogen carbonate solution. The solution wasdried over anhydrous magnesium sulfate and after separation of the spentdesiccant by filtration the methylene chloride was removed in vacuo.

26.1 g (theory, 29.9 g) of a light amber oil resulted. Analysis by highperformance LC indicated that there was less than 0.1% of residual2-hydroxy-4-(2-hydroxyethoxy)benzophenone in the product. The UVspectrum of the product was similar to that of2-hydroxy-4-(2-hydroxyethoxy)benzophenone, which showed that the desiredproduct was formed. Analysis bay ultraviolet (UV) spectroscopy showedthat the product contained about 29.8 weight % (theory, 30.1 weight %)of attached 2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonyloxy) UVabsorbing groups. Based on the method of preparation and analyses, theproduct formed in this reaction, I-19, was amono(2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonylamino) endcappedJeffamine® M-600 oligomer.

EXAMPLE 20 Endcapping of Jeffamine® D-400 with3,5-t-Butyl-4-hydroxybenzoyl Chloride (Compound I-20)

18.7 g (69.6 mmoles) of 3,5-di-t-butyl-4-hydroxybenzoyl chloride wereadded to 15.0 g (69.6 m.e.q.) of Jeffamine® D-400 (a diamino oligomericpolyether with a molecular weight of about 400 based on 7.43 weight %amino groups, produced by Texaco, Inc.) and 8.0 g (79.0 mmoles) oftriethylamine in 100 mL of dry methylene chloride, employing theprocedure used in Example 11. 26.9 g (theory, 31.2 g) of light yellowglassy material which contained less than 0.1 weight % residual3,5-di-t-butyl-4-hydroxybenzoic acid were obtained. An infrared (IR)spectrum of the product showed the expected absorption band at 1733 cm⁻¹for the carbonyl group. Based on the method of preparation and analyses,the product formed in this reaction, I-20, was abis(2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonylamino) endcappedJeffamine® D-400 oligomer.

EXAMPLE 21 Endcapping of Jeffamine® D-400 with3,5-Di-t-Butyl-4-hydroxybenzoic Acid and Methyl HydrogenTetrabromophthalate (Compound I-21a, I-21b and I-21c)

An Erlenmeyer flask was charged with 10.0 g (46.4 m.e.q.) of Jeffamine®D-400, 5.9 g (23.2 mmoles) of 3,5-di-t-butyl-4-hydroxybenzoic acid, 4.8g (23.3 mmoles) of dicyclohexylcarbodiimide, and 150 mL of drytetrahydrofuran. The reaction mixture was then stirred overnight at roomtemperature. Then the precipitated dicyclohexyl urea was filtered offand was washed with fresh tetrahydofuran. 11.5 g (23.2 mmoles) of methylhydrogen tetrabromophthalate were added to the combined tetrahydrofuransolutions. The resulting solution was concentrated and was placed in a160° C. vacuum oven for 15 hours.

A greenish yellow solid was obtained which contained 0.5 weight %residual tetrabromophthalic anhydride and 1.4 weight % of residual3,5-di-t-butyl-4-hydroxybenzoic acid according to high performance LC.An infrared (IR) spectrum of the product showed the expected absorptionband at 1734 cm⁻¹ for the carbonyl group. Based on the method ofpreparation and analyses, the product formed in this reaction was amixture of a bis(3,5-di-t-butyl-4-hydroxybenzoylamino) endcappedJeffamine® D-400 oligomer (I-21a), a bis(3,4,5,6-tetrabromophthalimido)endcapped Jeffamine® D-400 oligomer (I-21b) and amono(3,5-di-t-butyl-4-hydroxybenzoylamino),mono(3,4,5,6-tetrabromophthalimido) endcapped Jeffamine® D-400 oligomer(I-21c).

EXAMPLE 22 Reaction of the Sodium Alkoxy Salt of1,2,2,6,6-pentamethyl-4-piperidinol with TONE® 220 Bischloroformate(Compound I-22)

TONE® 220 bischloroformate was prepared from TONE® 220 and excessphosgene. At room temperature, 11.34 g (20.0 m.e.q.) of TONE® 220bischloroformate in 75 mL of dry methylene chloride was reacted with4.06 g (21.0 mmoles) of sodium 1,2,2,6,6-pentamethyl-4-piperidinoxide in41.5 g of toluene. The reaction mixture was stirred for 40 minutes atroom temperature, then washed twice with saturated aqueous sodiumhydrogen carbonate solution and twice with water. The solution was thendried over about 5% by weight of anhydrous magnesium sulfate and afterseparation of the spent desiccant, the solvent was removed in vacuo.

This left 14.1 g (theory, 14.0 g) of a light yellow viscous liquid.Analysis by gas chromatography (GC) showed that no residual1,2,2,6,6-pentamethyl-4-piperidinol was present. An infrared (IR)spectrum of the product showed the expected absorption bands at 1730cm⁻¹ and 1735 cm⁻¹ for the carbonyl groups. Based on the method ofpreparation and analyses the product formed in this reaction, I-22, wasa bis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyloxy) endcapped TONE®220 oligomer.

EXAMPLE 23 Reaction of the Sodium Alkoxy Salt of1,2,2,6,6-pentamethyl-4-piperidinol with Duracarb® 120 Bischloroformate(Compound I-23)

Duracarb® 120 bischloroformate was prepared from Duracarb® 120 andexcess phosgene. At room temperature, 9.4 g (20.0 m.e.q.) of Duracarb®120 bischloroformate in 150 mL of dry methylene chloride was reactedwith 4.32 g (22.0 mmoles) of sodium1,2,2,6,6-pentamethyl-4-piperidinoxide in 44.3 g of toluene. Thereaction mixture was stirred for 40 minutes at room temperature, thenwashed twice with saturated aqueous sodium hydrogen carbonate solutionand twice with water. The solution was then dried over about 5% byweight of anhydrous magnesium sulfate and after separation of the spentdesiccant, the solvent was removed in vacuo leaving 11.5 g (theory, 12.1g) of a yellow viscous liquid. An infrared (IR) spectrum of the productshowed the expected absorption band at 140 cm⁻¹ for the carbonyl groups.A chloroformate carbonyl band at 1780 cm⁻¹ was absent. Based on themethod of preparation and analyses, the product formed in this reaction,I-23, was a bis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyloxy)endcapped Duracarb® 120 oligomer.

EXAMPLE 24 Reaction of the Sodium Alkoxy Salt of1,2,2,6,6-pentamethyl-4-piperidinol with Other OligomericBischloroformates or Monochloroformates (Compounds I-24, I-25, I-26 andI-27)

Bischloroformates of Carbowax® 1000 (a poly(oxyethylene) diol oligomerhaving a molecular weight of 1000 manufactured by Union Carbide Corp.),Niax® 1025 (a poly(oxypropylene) diol oligomer having a molecular weightof 1000 manufactured by Union Carbide Corp.) a dihydroxy terminatedpolybutadiene (PBD) oligomer (having a molecular weight of about 2800manufactured by Scientific Polymer, Inc.), and the monochloroformate ofCarbowax® 2000 (a poly(oxyethylene) monohydroxyl oligomer having amolecular weight of 1900, manufactured by Union Carbide Corp.), weresynthesized by reacting the corresponding oligomeric diols ormono-hydroxyl oligomers with excess phosgene and isolation of thecorresponding bischloroformate (BCF) or monochloroformate (MCF) byremoving excess phosgene in vacuo. The reactions between thechloroformates and sodium 1,2,2,6,6-pentamethyl-4-piperidinoxide (SPPO)were carried out using the procedure set forth in Example 23. The tablebelow summaries the quantities of reactants and solvents employed andthe yield of bis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyloxy)endcapped oligomer formed in each case.

    ______________________________________                                        Solvent/                 Product Yield                                        Reactants Quantity       Theory, g Actual, g                                  ______________________________________                                        Carbowax 1000                                                                           1.125 g (2.0 meq.)                                                  BCF                                                                           SPPO      0.45 g  (2.3 mmol.)                                                                               1.4     0.6.sup.1 (I-24)                        Toluene   4.6 g                                                               Methylene 15 mL                                                               Chloride                                                                      Carbowax 2000                                                                           19.62 g (10.0 mmol.)                                                MCF                                                                           SPPO      2.26 g  (11.7 mmol.)                                                                             21.0    19.2.sup.2 (I-25)                        Toluene   23.1 g                                                              Methylene 75 mL                                                               Chloride                                                                      Niax 1025 BCF                                                                           22.64 g (40 meq.)                                                   SPPO      8.10 g  (42.0 mmol.)                                                                             28.0    24.1.sup.3 (I-26)                        Toluene   83.1 g                                                              Methylene 75 mL                                                               Chloride                                                                      PBD BCF   29.95 g (20 meq.)                                                   SPPO      4.06 g  (21.0 mmol.)                                                                             31.9    31.6.sup.4 (I-27)                        Toluene   41.5 g                                                              Methylene 75 mL                                                               Chloride                                                                      ______________________________________                                         .sup.1 A yellow paste, IR spectrum showed carbonate carbonyl band at 1738     cm.sup.-1.                                                                    .sup.2 A white waxy solid, IR spectrum showed carbonate carbonyl band at      1740 cm.sup.-1. GC showed no presence of                                      1,2,2,6,6pentamethyl-4-piperidinol                                            .sup.3 Viscous oil, IR spectrum showed no presence of starting                bischloroformate.                                                             .sup.4 Resinous material, IR spectrum showed the presence of a carbonate      carbonyl band at 1738 cm.sup.-1 and the absence of a chloroformate band a     1775 cm.sup.-1.                                                          

Based on the method of preparation and analyses, I-24 was abis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyloxy) endcapped Carbowax®1000 oligomer.

Based on the method of preparation and analyses, I-25 was amono(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyloxy) endcappedCarbowax® 2000 oligomer.

Based on the method of preparation and analyses, I-26 was abis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyloxy) endcapped Niax°1025 oligomer.

Based on the method of preparation and analyses, I-27 was abis(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonyloxy)endcappedpolybutadiene (PBD) oligomer.

EXAMPLE 25 Reaction of the Sodium Alkoxy Salt of2,2,6,6-tetramethyl-4-piperidinol with Carbowax® 1000 Bischloroformate(Compounds I-28a and I-28b)

Using the procedure outlined in Example 11, 3.5 g (22.0 mmoles) of2,2,6,6-tetramethyl-4-piperidinol, 2.4 g (30.0 mmoles) of pyridine and15 mL of methylene chloride were reacted with 11.2 g (20.0 mequivalents)of the bischloroformate of Carbowax® 1000. After the work-up, two waxysolids were obtained. One (I-28a), 4.5 g (theory, 13.6 g), as thedesired product, the bis(2,2,6,6-tetramethyl-4-piperidinoxycarbonyloxy)endcapped Carbowax® 1000, and the second (I-28b), 6.3 g, was thecarbonate-carbamate polymer resulting from reaction of Carbowax® 1000BCF with both the hydroxy group in the `4` position and the hinderedamine group in the `1` position of 2,2,6,6-tetramethyl-4-piperidinol.The desired product had a carbonate carbonyl band at 1745 cm³¹ 1.

EXAMPLE 26 Preparation of Sulfonic Acid Salt Oligomers Using EthylAcetate as the Solvent (Compounds I-1, I-29, I-30 and I-31)

General Procedure: A 1 L three-neck flask was charged with about 400 mLof dry ethyl acetate, 8.5 g (80 mmoles) of anhydrous sodium carbonateand sufficient oligomeric diols as indicated in the Table below for 50m.e.q. of hydroxyl groups. The mixture was magnetically stirred and waspurged with nitrogen for 2-3 minutes prior to addition of 12.2 g (60.9mmoles) of 97% 2-sulfobenzoic acid cyclic anhydride in one portion. Theresultant suspension was heated to reflux until the evolution of CO₂ hadceased (ca. 90 minutes). The reaction mixture was cooled to about 45° C.and was washed once with about 250 mL of 33% monosodium dihydrogenphosphate solution. The liquid phases were allowed to separate and, ifnecessary, additional ethyl acetate was added to aid the separation. Thelower aqueous layer was separated and discarded and the solvent wasremoved from the product layer to yield the desired products. Theproducts obtained from the reaction with the various oligomers are setforth in the following Table.

    ______________________________________                                                       Product Yield                                                  Oligomer Used                                                                            Quantity, g                                                                             Theory, g Actual, g                                                                            Product                                 ______________________________________                                        TONE ® 260                                                                           75.0      85.3      90.2   I-1                                     TONE ® 240.sup.1                                                                     50.0      60.4      58.5   I-29                                    TONE ® 210.sup.2                                                                     20.8      31.5      27.7   I-30                                    Duracarb ® 122.sup.3                                                                 21.2      32.0      28.0   I-31                                    ______________________________________                                         .sup.1 An oligomeric polycaprolactone based diol, having a molecular          weight of ca. 2000 based on a hydroxyl content of 1.72%, manufactured by      Union Carbide Corporation                                                     .sup.2 An oligomaric polycaprolactone based diol, having a molecular          weight of ca. 800 based on a hydroxyl content of 4.12%, manufactured by       Union Carbide Corporation                                                     .sup.3 An aliphatic polycarbonate oligomeric diol, having a molecular         weight of about 1000 based on a hydroxyl content of 3.52 weight %,            manufactured by PPG Industries, Inc.                                     

Example 27 relates to flame retardant testing of a polycarbonate blendedwith flame retardant oligomeric compounds of the present invention. Thepolycarbonate selected is believed to be representative of the flameretardant properties provided by the general category of flame retardantoligomers of the present invention not only with respect to theparticular polycarbonate used in the test but also with respect topolycarbonates in general, as well as other engineering thermoplasticpolymeric resins.

EXAMPLE 27 Flame Retardant Testing of Bisphenol A Polycarbonate (PC)containing Invention Flame Retardant Additives

Dow Calibre® 300-6 (referred to generally hereinafter as "300-6" generalpurpose bisphenol A polycarbonate (PC) (weight average molecular weightof about 55,000; intrisic viscosity of 0.507 dL/g at 25° C. in methylenechloride) was blended with various levels of oligomeric compounds of thepresent invention (I-1 from Example 1, I-2 from Example 2 and I-3 fromExample 5), employing the following procedure:

Pellets of 300-6 PC were dried in an oven at 125° C. for 4 hours. Therequired amount (as indicated in Table 1 below) of I-1 was melted,poured onto the hot 300-6 pellets and the resulting composition wasthoroughly hand-mixed while the composition cooled to some extent. Whilestill cooling, the 300-6 PC-I-1 blend was extruded at 280° C. through aone and a quarter inch Brabender Extruder having a length to diameterratio of 25 to 1. The extruded composition was then dried again in anoven at 125° C. for 4 hours just prior to molding into desired testspecimens using either a Newberry or Stokes injection molding machinewith an appropriate mold.

Notched Izod tests (ASTM D-256) at room temperature and at 30° F. Meltflow index tests (ASTM D-1238, condition "O") and UL-94 burning testswere carried out on appropriate specimens of 300-6 PC blended with 0.0%(control), 0.125%, 0.250%, 0.50%, 1.0% and 1.5% of I-1. The results ofthese tests are set forth in Example 27--Table 1.

Also tested were Dow Calibre® 700-6 ignition resistant grade PC(hereinafter "700-6") and 300-6 PC compounded with 2.0% I-2 (fromExample 2) and 2.0% I-3 (from Example 5) using the procedures set forthabove. The results of this work are summarized in Example 27--Table 2.

                  TABLE 1                                                         ______________________________________                                        Example 27                                                                    Dow PC                                                                        Additive Level, %                                                                         300-6                                                             ______________________________________                                        I-1         0.0    0.125   0.250 0.50 1.0  1.5                                Notched Izod                                                                              17.7   17.6    17.3  17.4 17.5 17.1                               Rm Temp, Ft-lb/in                                                             Notched Izod                                                                              17.7   17.5    17.0  17.0 16.3 12.3                               30° F., Ft-lb/in                                                       Melt Flow Index,                                                                          5.3    5.6     6.0   6.6  7.4  8.4                                grams/10 mins.                                                                UL-94 Rating                                                                              V-2    V-0     V-0   V-0  V-0  V-0                                (1/8 inch specimens)                                                          ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Example 27                                                                    Dow PC                                                                        Additive Level, %                                                                            300-6      300-6  700-6                                        ______________________________________                                        I-2             2.0       --     --                                           I-3            --         2.0    --                                           None           --         --     0.0                                          Notched Izod   16.9       --     --                                           Rm Temp, Ft-lb/in                                                             Notched Izod   --         --     --                                           30° F., Ft-lb/in                                                       Melt Flow Index,                                                                             10.9       9.9    --                                           grams/10 mins.                                                                UL-94 Rating   V-0        V-0    V-0                                          (1/8 inch specimens)                                                          ______________________________________                                    

These results show that the invention oligomers of the presentinvention, i.e., I-1, I-2 and I-3, convey highly desirable V-0 ratings(UL-94 tests) to a general purpose bisphenol PC (300-6) withoutdetrimentally affecting physical properties such as notched izod or meltflow. In addition, very low levels are effective in conveying V-0ratings to 300-6 PC, e.g., 0.125% I-1. These results are in contrast tothe teachings of the prior art. Briefly, a classification of the UL-94test results is as follows:

UL-94 V-2: No test specimen may burn for more than 30 seconds, and thetotal burn time for five test specimens may not exceed 250 seconds. Thetest specimens may have drips that burn.

UL-94 V-1: No test specimen may burn for more than 30 seconds, and thetotal burn time for five test specimens may not exceed 250 seconds. Thetest specimens may not have drips that burn.

UL-94 V-0: No test specimen may burn for more than 10 seconds, and thetotal burn time for five test specimens may not exceed 50 seconds. Thetest specimens may not have drips that burn.

Thus, the prior art on flame retarding PC's indicates that both asulfonic acid salt as well as a bromine compound are necessary foreffective flame retardance of PC's. In fact, Dow Chemical Co.'s ignitionresistant grade PC (i.e., 700-6) contains both a salt and a brominecompound. The inventors have surprisingly found that a very low level ofI-1, a novel flame retardant oligomer of this invention, is effectivewithout a bromine compound in flame retarding PC.

The following Examples 28 through 32 illustrate the preparation ofvarious sulfobenzoic acid compounds and derivatives generallycorresponding to the compound of Structure C set forth above. The samegeneral preparative techniques typically would be used to prepare othercompounds and derivatives under the broad definition of Structure C.Variations would be well known to those of ordinary skill in the art.

EXAMPLE 28 Preparation of 2-Sulfobenzoic Acid Monosodium Salt (Compound(I-32)

20 g (108.6 mmoles) of 2-sulfobenzoic acid cyclic anhydride were addedto a beaker containing 250 mL of water. After the reactant dissolved,4.4 g (110 mmoles) of sodium hydroxide were added. After the water wasremoved, 22.9 g (94% of theory) of a white powder product, I-32, thetitle compound, were recovered.

EXAMPLE 29 Preparation of 2-Sulfobenzoic Acid Methyl Ester, Sodium Salt(Compound I-33)

A flask containing 150 mL of methanol was charged with 20.3 g (110mmoles) of 2-sulfobenzoic acid cyclic anhydride. The anhydride quicklydissolved with evolution of heat. Then, 4.4 g (110 mmoles) of sodiumhydroxide were added. After the sodium hydroxide dissolved, the excessmethanol was removed to yield 23 g (100% of theory) of a white powderproduct, I-33, the title compound.

EXAMPLE 30 Preparation of 2-Sulfobenzoic Acid Octyl Ester, Sodium Salt(Compound I-34)

20.2 g (109.2 mmoles) of 2-sulfobenzoic acid cyclic anhydride were addedto a flask containing 75 g (576 mmoles) of 1-octanol. The magneticallystirred mixture was warmed to 30° C. for 30 minutes to yield a slightlyhazy solution. Then, 4.6 g (115 mmoles) of sodium hydroxide, dissolvedin 20 mL of water, were added to the 1-octanol solution. A clearsolution resulted. Then as much of the excess 1-octanol as possible wasremoved under reduced pressure. The resulting white paste was slurriedin 300 mL of hexane and filtered. The resulting white solid was dried toa constant weight in a 40° C. vacuum oven to yield 33.6 g (96.8% oftheory) of dry product, I-34, the title compound.

EXAMPLE 31 Preparation of 2-Sulfobenzoic Acid 4-Phenyl-Phenyl Ester,Sodium Salt (Compound I-35)

20.6 g (112 mmoles) of 2-sulfobenzoic acid cyclic anhydride and 18.5 g(109 mmoles) o 4-phenyl-phenol were added to a flask containing 300 mLof toluene. The stirred mixture was warmed to 60° C. for 30 minutes. Asomewhat hazy solution resulted which was filtered hot through a coarsefritted glass filter to yield a clear solution. Upon cooling, aprecipitate formed, which was redissolved after warming to 60° C. When4.6 g (115 mmoles) of sodium hydroxide in 25 mL of water were added tothe warm solution, a heavy precipitate immediately formed. After 30minutes of additional stirring, the solid was filtered while hot and waswashed with toluene. The product was then dried to a constant weight ina 70° C. vacuum oven to yield 31.5 g (79% of theory) of a white powderproduct, I-35, the title compound.

EXAMPLE 32 Preparation of 2-Sulfobenzoic Acid2,2,3,4,4,4-Hexafluoro-1-butyl Ester, Sodium Salt (Compound I-36)

15.0 g (82.4 mmoles) of 2,2,3,4,4,4-hexafluorobutan-1-ol and 10.0 g (54mmoles) of 2-sulfobenzoic acid cyclic anhydride were added to 50 mL ofdry methylene chloride. The mixture was heated to reflux for severalhours. The resulting clear solution was cooled to room temperature andwas neutralized with 2.2 g (55 mmoles) of sodium hydroxide in 20 mL ofwater. The solvent was removed and the resultant solid was dried toconstant weight in a 60° C. vacuum oven. 17.5 g (83.5% of theory) of awhite powder product, I-36, the title compound, were obtained.

The following Example 33 relates to flame retardant testing of apolycarbonate which has been blended with various oligomeric sulfonicacid salt derivatives and various monomeric sulfonic acid saltderivatives according to the present invention. The test procedures andcompounds tested are believed to be typical of the procedures used andresults which would be obtained if other compounds according to thepresent invention were tested as would be well known by one of ordinaryskill in the art.

EXAMPLE 33 Flame Retardant Testing of Bisphenol A Polycarbonate (PC)containing Invention Flame Retardant Additives

The oligomeric salts of Example 26 (I-1, I-29, I-30 and I-31) werecompounded into Dow's 300-6 general purpose PC according to theprocedure described in Example 27 using the amounts set forth in Example33--Table 1 below. The salts of the monomeric sulfobenzoic acidcompounds from Examples 29 through 32 were added as dry powders in anamount of 0.2%, based n the weight of the PC, to dry PC which had beenpreviously coated with 0.1 weight % mineral oil. The coated pellets werethen extruded and molded as described in Example 27. UL-94 and OxygenIndex (ASTM Procedure D 2863) tests were then carried out on the moldedspecimens. The results are summarized in Example 33, Tables 1 and 2.

                  TABLE 1                                                         ______________________________________                                        Example 33                                                                    UL-94 and Oxygen Index Test Results for Oligomeric Sulfonic                   Acid Salt Derivatives in Bisphenol A PC                                       Additive Level, %   UL-94 Rating                                                                             Oxygen Index                                   ______________________________________                                        None     --         V-2        26                                             I-1      0.2        V-1        32                                             I-29     0.2        V-0        35                                             I-30     0.2        V-0        37                                             I-31     0.2        V-0        36                                             I-1*     0.2        V-0        36                                             I-29*    0.2        V-0        37                                             I-30*    0.2        V-0        40                                             I-1      0.1        V-1        30                                             I-29     0.1        V-0        34                                             I-30     0.1        V-0        33                                             I-1       0.05      V-2        28                                             I-29      0.05      V-0        31                                             I-30      0.05      V-0        32                                             ______________________________________                                         *In combination with 0.6% Decabromodiphenyl Ether                        

                  TABLE 2                                                         ______________________________________                                        Example 33                                                                    UL-94 and Oxygen Index Test Results for Monomeric Sulfonic                    Acid Salt Derivatives in Bisphenol A PC                                       Additive Level, %   UL-94 Rating                                                                             Oxygen Index                                   ______________________________________                                        None     --         V-2        26                                             I-32     0.2        V-0        33                                             I-33     0.2        V-0        34                                             I-34     0.2        V-0        34                                             I-35     0.2        V-0        36                                             I-36     0.2        V-0        35                                             ______________________________________                                    

Briefly, a classification of the UL-94 test results is as follows:

UL-94 V-2: No test specimen may burn for more than 30 seconds, and thetotal burn time for five test specimens may not exceed 250 seconds. Thetest specimens may have drips that burn.

UL-94 V-1: No test specimen may burn for more than 30 seconds, and thetotal burn time for five test specimens may not exceed 250 seconds. Thetest specimens may not have drips that burn.

UL-94 V-0: No test specimen may burn for more than 10 seconds, and thetotal burn time for five test specimens may not exceed 50 seconds. Thetest specimens may not have drips that burn.

The Oxygen Index Number is the volume percent of oxygen in anoxygen-nitrogen mixture that is necessary to maintain burning of thetest specimen. The volume percent oxygen in a normal atmosphere is 21.Thus, the higher the Oxygen Index Number, the more flame retardant acomposition is.

Clearly, the test results demonstrate that the sulfonic acid saltderivatives of this invention have significantly improved the ignitionresistance of the polycarbonate with which they have been blended.

The present invention may be embodied in other specific forms withoutdeparting from the spirit or essential attributes thereof and,accordingly, reference should be made to the appended claims, ratherthan to the foregoing specification as indicating the scope of theinvention.

We claim:
 1. An oligomeric performance additive compound having at leastone functional performance group, the compound having a structure A:##STR26## y=0 to 75, Z1, Z2 and Z3 are the same or different with theproviso that at least one of Z1, Z2 and Z3 is selected from the groupconsisting of at least one of performance additive functional group I,II and III, whereinperformance additive functional group I is anantioxidant monoradical having a structure selected from the groupconsisting of structure (1), (2) and (3); ##STR27## where X is selectedfrom the group consisting of NH and O, R1 and R2 are the same ordifferent and each is selected from the group consisting of an alkylradical of 1 to 13 carbons and a t-aralkyl radical of 9 to 13 carbons,R11 is a alkylene diradical of 1 to 6 carbons, and z is 0 or 1;##STR28## where R3 is selected from the group consisting of an alkylradical of 1 to 18 carbons, an aryl radical of 6 to 12 carbons and anaralkyl radical of 7 to 11 carbons; and ##STR29## where R3 and R3' arethe same or different, and R3' is selected from the group consisting ofan alkyl radical of 1 to 18 carbons, an aryl radical of 6 to 12 carbonsand an aralkyl radical of 7 to 11 carbons; performance additivefunctional group II is a UV stabilizing monoradical having a structureselected from the group consisting of structure (1), (2), (3) and (4):##STR30## where X1 is selected from the group consisting of nothing andO, and R_(b) is selected from the group consisting of hydrogen and asubstituent selected from the group consisting of a lower alkyl radical,a lower alkoxy radical, a cyano radical, chloro, bromo and nitro;##STR31## where R_(b') is selected from the group consisting of hydrogenand a substituent selected from the group consisting of a lower alkylradical, a t-octyl radical, an alpha-cumyl radical, a lower alkoxyradical, a cyano radical, chloro, bromo and nitro; and performanceadditive functional group III is a light stabilizing monoradical havinga structure: ##STR32## where X and X2 are the same or different and eachis selected from the group consisting of NH and O, and R4 is selectedfrom the group consisting of H, a lower alkyl radical, an acyl radicalof 2 to 18 carbons, an aroyl radical of 7 to 15 carbons, analkoxycarbonyl radical of 2 to 19 carbons, and an aryloxycarbonylradical of 7 to 15 carbons; any other of Z1, Z2 and Z3 not selected fromthe group consisting of performance additive functional groups I, II andIII is selected from the group consisting of hydroxy, amino, at leastone substituted radical and an unsubstituted radical, where the radicalis selected from the group consisting of an alkoxy radical of 1 to 12carbons, an alkylamino radical of 1 to 12 carbons, an acyloxy radical of1 to 12 carbons, an acylamino radical of 1 to 12 carbons, an alkenoyloxyradical of 3 to 12 carbons, an alkenoylamino radical of 3 to 12 carbons,an aroyloxy radical of 7 to 15 carbons, an aroylamino radical of 7 to 15carbons, a phthalimido radical, an alkoxycarbonyloxy radical of 2 to 13carbons, an alkoxycarbonylamino radical of 2 to 13 carbons, analkenyloxycarbonyloxy radical of 3 to 12 carbons, analkenyloxycarbonylamino radical of 3 to 12 carbons, anaryloxycarbonyloxy radical of 7 to 15 carbons, an aryloxycarbonylaminoradical of 7 to 15 carbons, an alkylaminocarbonyloxy radical of 2 to 13carbons, an arylaminocarbonyloxy radical of 7 to 15 carbons, anaralkylaminocarbonyloxy radical of 7 to 16 carbons, an alkylsulfonyloxyradical of 1 to 8 carbons, an alkylsulfonylamino radical of 1 to 8carbons, an arylsulfonyloxy radical of 6 to 11 carbons, anarylsulfonylamino radical of 6 to 11 carbons, a perfluoroacyloxy radicalof 2 to 14 carbons, and a perfluoroacylamino radical of 2 to 14 carbons;where the substituents thereof are selected from the group consisting ofCl, Br, an acetyl radical, an alkyl radical of 1 to 6 carbons, analkenyl radical of 2 to 6 carbons, an aryl radical of 6 to 10 carbons,an alkoxy radical of 1 to 6 carbons, an aryloxy radical of 6 to 10carbons, an alkoxycarbonyl radical of 2 to 13 carbons, ahydroxyalkoxycarbonyl radical of 3 to 13 carbons, achlorohydroxyalkoxycarbonyl radical of 4 to 13 carbons, and anepoxyalkoxycarbonyl radical of 4 to 13 carbons; A1, A2 and A3 arenothing, the same or different, with the proviso that when A3 isnothing, only one of A1 and A2 can be nothing, and when y=0, A2 isnothing, and A1 is selected from the group consisting of diradicals (1),(2) and (3): ##STR33## where R33 is selected from the group consistingof an alkylene diradical of 2 to 8 carbons and an alkylene diradical of2 to 8 carbons containing at least one atom selected from the groupconsisting of O, S and N atoms in the alkylene chain, (Z1) and (Z2) showthe relationship of the --A1--diradical to Z1 and Z2, respectively, andthe sum of k and m is 3 to 50; ##STR34## where (Z1) and (Z2) show therelationship of the --A1--diradical to Z1 and Z2, respectively, and n1is 5 to 20; and (3) an oligomeric diradical selected from the groupconsisting of an oligomeric polybutadiene diradical, an oligomericaromatic polyester diradical, an oligomeric aliphatic polyurethanediradical and an oligomeric aliphatic polyurea diradical; and when atleast one of Z1 and Z2 are selected from performance additive group IIIand when two of Z1 and Z2 are each selected from different performanceadditive functional groups I, II and III, A1 can additionally beselected from (4): ##STR35## wherein R4' is selected from the groupconsisting of H and a lower alkyl radical, (Z1) and (Z2) show therelationship of the --A1--diradical to Z1 and Z2, respectively, and n4is 2 to 70; and when y is 1, the triradical ##STR36## has a structure##STR37## where (Z1), (Z2) and (Z3) show the relationship of thetriradical to Z1, Z2 and Z3, respectively, R7 is selected from the groupconsisting of H and an alkyl radical of 1 to 6 carbons, R44 is selectedfrom the group consisting of nothing and an alkylene diradical of 1 to 6carbons, and the sum of k1, m1 and p1 is 2 to 20; when y is 2 to 75, A1has a structure: ##STR38## where R8 is selected from the groupconsisting of a phenyl radical and an acetoxy radical and s1 is 4 to 25;and when y is 2 to 74, A2 and A3 are nothing, and triradical R has astructure: ##STR39## where R9 is selected from the group consisting ofnothing and a methylene diradical, (Z3) shows the relationship betweenthe triradical R group and Z3; the compound of Structure A beingpreparable from a compound of Structure B: ##STR40## where T is selectedfrom the group consisting of H and a halocarbonyl radical; where thecompound of Structure B is reacted with a performance additive compoundpossessing at least one co-reactive group selected from the groupconsisting of a hydroxy radical, an amino radical, an epoxide radical, acarboxylic acid cyclic anhydride radical, a sulfocarboxylic cyclic acidanhydride radical, a haloformate radical and an isocyanate radical.
 2. Aprocess for enhancing UV stability, light stability and/or oxidativestability of an engineering thermoplastic polymeric resin compositioncomprising mixing with the engineering thermoplastic polymeric resincomposition about 0.05% to about 10% by weight, based on the weight ofthe engineering thermoplastic polymeric resin composition, of anoligomeric performance additive compound of Structure A according toclaim 1, at about 100° C. to about 550° C., until intimately mixed.
 3. Aprocess according to claim 2 wherein the mixing is at a temperature ofabout 150° C. to about 400° C.
 4. A process according to claim 2 whereinthe engineering thermoplastic polymeric resin composition is selectedfrom the group consisting of aromatic polycarbonates; aromaticpolycarbonates blended with styrene maleic anhydride copolymers;aromatic polycarbonates blended with acrylonitrile butadiene styrenecopolymers; polyethylene terphthalate; polybutylene terephthalate;polyphenylene oxide; polyphenylene oxide blended with polystyrene;polyphenylene oxide blended with high impact polystyrene; styrene maleicanhydride copolymers; acrylonitrile butadiene styrene copolymers; blendsof polyethylene terphthalate and polybutylene terephthalate; nylons andpolysulfones.
 5. A composition comprising about 90% to about 99.95% ofan engineering thermoplastic polymeric resin composition and about 0.05%to about 10% by weight, based on the weight of the engineeringthermoplastic polymeric resin composition, of an oligomeric performanceadditive compound of Structure A according to claim
 1. 6. A compositionaccording to claim 5 wherein the engineering thermoplastic polymericresin composition is selected from the group consisting of aromaticpolycarbonates; aromatic polycarbonates blended with styrene maleicanhydride copolymers; aromatic polycarbonates blended with acrylonitrilebutadiene styrene copolymers; polyethylene terphthalate; polybutyleneterphthalate; polyphenylene oxide; polyphenylene oxide blended withpolystyrene; polyphenylene oxide blended with high impact polystyrene;styrene maleic anhydride copolymers; acrylonitrile butadiene styrenecopolymers; blends of polyethylene terphthalate and polybutyleneterephthalate; nylons and polysulfones.
 7. A compound according to claim1 wherein at least one of Z1, Z2 and Z3 is an antioxidant monoradicalhaving the structure: ##STR41## where R1 and R2 are the same ordifferent and are selected from the group consisting of a t-alkylradical of 4 to 8 carbons and a t-aralkyl radical of 9 to 13 carbons;andR11 is selected from the group consisting of an alkylene diradical of1 to 3 carbons; z is
 1. 8. An oligomeric performance additive compoundhaving at least one functional performance group, the compound having astructure A: ##STR42## where y=0 to 75,Z1, Z2 and Z3 are the same ordifferent with the proviso that at least one of Z1, Z2 and Z3 is anantioxidant monoradical performance additive functional group having astructure selected from the group consisting of structure (1), (2) and(3): ##STR43## where X is selected from the group consisting of NH andO, R1 and R2 are the same or different and each is selected from thegroup consisting of an alkyl radical of 1 to 13 carbons and a t-aralkylradical of 9 to 13 carbons, R11 is selected from the group consisting ofnothing and an alkylene diradical of 1 to 6 carbons, and z is 0 or 1;##STR44## where r3 is selected from the group consisting of an alkylradical of 1 to 18 carbons, an aral radical of 6 to 12 carbons and anaralkyl radical of 7 to 11 carbons; and ##STR45## where R3 and R3' arethe same or different, and r3' is selected from the group consisting ofan alkyl radical of 1 to 18 carbons, an aryl radical of 6 t 12 carbonsand an aralkyl radical of 7 to 11 carbons; any other of Z1, Z2 and Z3not selected from the group consisting of antioxidant monoradicals (1),(2) and (3) is selected from the group consisting of hydroxy, amino, atleast one substituted radical and an unsubstituted radical, where theradical is selected from the group consisting of an alkoxy radical of 1to 12 carbons, an alkylamino radical of 1 to 12 carbons, an acyloxyradical of 1 to 12 carbons, an alkenoyloxy radical of 3 to 12 carbons,an alkenoylamino radical of 3 to 12 carbons, an aroyloxy radical of 7 to15 carbons, an aroylamino radical of 7 to 15 carbons, a phthalimidoradical, an alkoxycarbonyloxy radical of 2 to 13 carbons, analkoxycarbonylamino radical of 2 to 13 carbons, an alkenyloxycarbonyloxyradical of 3 to 12 carbons, an alkenyloxycarbonylamino radical of 3 to12 carbons, an aryloxycarbonyloxy radical of 7 to 15 carbons, anaryloxycarbonylamino radical of 7 to 15 carbons, analkylaminocarbonyloxy radical of 2 to 13 carbons, anarylaminocarbonyloxy radical of 7 to 15 carbons, anaralkylaminocarbonyloxy radical of 7 to 16 carbons, an alkylsulfonyloxyradical of 1 to 8 carbons, an alkylsulfonylamino radical of 1 to 8carbons, an arylsulfonyloxy radical of 6 to 11 carbons, anarylsulfonylamino radical of 6 to 11 carbons, a perfluoroacyloxy radicalof 2 to 14 carbons, and a perfluoroacylamino radical of 2 to 14 carbons;where the substituents thereof are selected from the group consisting ofCl, Br, an acetyl radical, an alkyl radical of 1 to 6 carbons, analkenyl radical of 2 to 6 carbons, an aryl radical of 6 to 10 carbons,an alkoxy radical of 1 to 6 carbons, an aryloxy radical of 6 to 10carbons, an alkoxycarbonyl radical of 2 to 13 carbons, ahydroxyalkoxycarbonyl radical of 3 to 13 carbons, achlorohydroxyalkoxycarbonyl radical of 4 to 13 carbons, and anepoxyalkoxycarbonyl radical of 4 to 13 carbons; A1, A2 and a3 arenothing, the same or different, with the proviso that when A3 isnothing, only one of A1 and A2 can be nothing, and when y=1, A2 isnothing, and A1 is selected from the group consisting of diradicals (1),(2) and (3); ##STR46## where R33 is selected from the group consistingof an alkylene diradical of 2 to 8 carbons and an alkylene diradical of2 to 8 carbons containing at least one atom selected from the groupconsisting of O, S and N atoms in the alkylene chain, (Z1) and (Z2) showthe relationship of the --A--diradical to Z1 and Z2, respectively, andthe sum of k and m is 3 to 50; ##STR47## where (Z1) and (Z2) show therelationship of the --A1--diradical to Z1 and Z2, respectively, and n1is 5 to 20; and (3) an oligomeric diradical selected from the groupconsisting of an oligomeric polybutadiene diradical, an oligomericaromatic polyester diradical, an oligomeric aliphatic polyurethanediradical, an oligomeric aliphatic polyurea diradical; and when y is 1,the triradical ##STR48## has a structure: ##STR49## where (Z1), (Z2) and(Z3) show the relationship of the triradical to Z1, Z2 and Z3,respectively, R7 is selected from the group consisting of H and an alkylradical of 1 to 6 carbons, R4 is selected from the group consisting ofnothing and an alkylene diradical of 1 to 6 carbons, and the sum of k1,m1 and p1 is 2 to 20; when y is 2 to 75, A1 has a structure: ##STR50##where R8 is selected from the group consisting of a phenyl radical andan acetoxy radical and s1 is 4 to 25; and when y is 2 to 75, A2 and A3are nothing, and triradical R has a structure: ##STR51## where R9 isselected from the group consisting of nothing and a methylene diradical,(Z3) shows the relationship between the triradical R group and Z3; thecompound of Structure A being preparable from a compound of Structure B:##STR52## where T is selected from the group consisting of H and ahalocarbonyl radical; where the compound of Structure B is reacted witha performance additive compound possessing at least one co-reactivegroup selected from the group consisting of a hydroxy radical, an aminoradical, an epoxide radical, a carboxylic acid cyclic anhydride radical,a sulfocarboxylic cyclic acid anhydride radical, a haloformate radicaland an isocyanate radical.